CN116282130A - Self-supporting nitrogen-doped carbon/ZnS flexible composite material and preparation method and application thereof - Google Patents
Self-supporting nitrogen-doped carbon/ZnS flexible composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 87
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 81
- 239000004814 polyurethane Substances 0.000 claims abstract description 68
- 229920002635 polyurethane Polymers 0.000 claims abstract description 68
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims abstract description 24
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims abstract description 4
- SLCITEBLLYNBTQ-UHFFFAOYSA-N CO.CC=1NC=CN1 Chemical compound CO.CC=1NC=CN1 SLCITEBLLYNBTQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000003763 carbonization Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 8
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- KUJOABUXCGVGIY-UHFFFAOYSA-N lithium zinc Chemical compound [Li].[Zn] KUJOABUXCGVGIY-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/625—Carbon or graphite
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- 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
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention discloses a self-supporting nitrogen-doped carbon/ZnS flexible composite material, a preparation method and application thereof, wherein zinc salt is dissolved in methanol and added into polyurethane sponge methanol dispersion liquid, after being stirred and mixed uniformly, 2-methylimidazole methanol solution is added, stirring and reacting are carried out at room temperature, and the resultant is washed by methanol and baked in vacuum to obtain ZIF-8/polyurethane composite material; adding the ZIF-8/polyurethane composite material and thioacetamide into a methanol/water mixed solution, stirring uniformly under an argon atmosphere, heating to 50-70 ℃, stirring for 4-10 hours, washing and drying to obtain a ZnS/polyurethane composite material, carbonizing at a high temperature under a nitrogen atmosphere, and cooling to obtain the ZnS/nitrogen-doped carbon foam composite material. The raw materials for preparing the self-supporting nitrogen-doped carbon/ZnS flexible composite material are economical and environment-friendly, the preparation process is relatively simple, the cost is low, and the conductivity and the cycling stability of ZnS can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to a self-supporting nitrogen-doped carbon/ZnS flexible composite material, and a preparation method and application thereof.
Background
The lithium ion battery is expected to be widely applied to the wearable electronic energy storage device by virtue of high energy density and excellent cycle performance, but the traditional lithium ion battery is difficult to be directly applied to the wearable electronic energy storage device due to the dependence of electrode materials on metal current collectors and the characteristics of powder materials. It has become a hot spot problem in this research field to seek simple, efficient, low cost, environmentally friendly electrode preparation to meet the demands of flexible batteries.
Currently, commercial lithium ion anode materials are mainly carbon materials, which have many limitations: the theoretical capacity is low, dendrites and the like may be generated on the surface when the potential is close to that of the metal lithium, and the safety performance cannot be ensured. Therefore, searching for a battery anode material with higher capacity and more outstanding stability to replace the commercialized graphite anode is an important problem to be solved by scientific researchers. Among them, transition metal sulfides are receiving great attention as a negative electrode material for graphite replacement due to their high specific capacity and suitable operating potential. ZnS has the advantages of high theoretical capacity, no toxicity, low cost and the like, and is one of the most attractive lithium ion battery cathode materials at present. Based on the conversion and alloying reaction of ZnS into lithium zinc alloy and lithium sulfur, up to 825mAhg can be obtained −1 Is a theoretical specific capacity of (c). However, the capacity of pure ZnSThe attenuation is great, due to its drastic change in volume during lithium storage and the consequent pulverization of the zinc sulphide particles. In addition, the low conductivity of ZnS leads to retardation of electron transfer kinetics, thereby limiting the rate performance of lithium storage. Notably, znS materials lacking a conductive matrix and electron transfer pathway also typically suffer from poor electrochemical activity.
Disclosure of Invention
Aiming at the problems of large ZnS capacity attenuation and poor lithium storage multiplying power performance in the prior art, the invention provides a self-supporting nitrogen-doped carbon/ZnS flexible composite material, a preparation method and application thereof, which can exert the respective advantages of ZnS and nitrogen-doped carbon foam and effectively improve the conductivity and the circulation stability of ZnS.
The invention is realized by the following technical scheme:
the preparation method of the self-supporting nitrogen-doped carbon/ZnS flexible composite material is characterized by comprising the following steps of:
(1) Preparation of ZIF-8/polyurethane composite material: dissolving zinc salt in methanol, adding the dissolved zinc salt into polyurethane sponge methanol dispersion liquid, stirring and mixing uniformly, adding 2-methylimidazole methanol solution, stirring and reacting at room temperature, washing a product with methanol, and baking in vacuum to obtain ZIF-8/polyurethane composite material;
(2) Preparation of ZnS/polyurethane composite: adding the ZIF-8/polyurethane composite material prepared in the step (1) and thioacetamide into a methanol/water mixed solution, uniformly stirring under an argon atmosphere, heating to 50-70 ℃, stirring for 4-10 hours, washing and drying to obtain a ZnS/polyurethane composite material;
(3) Preparation of self-supporting nitrogen-doped carbon/ZnS flexible composite: and (3) carbonizing the ZnS/polyurethane composite material prepared in the step (2) at a high temperature in a nitrogen atmosphere, and cooling to obtain the ZnS/nitrogen-doped carbon foam composite material.
Further, the zinc salt in the step (1) is Zn (NO) 3 ) 2 .6H 2 O，Zn(NO 3 ) 2 .6H 2 The mass ratio of O to polyurethane sponge is 1:10-10:1, zn (NO) 3 ) 2 .6H 2 The mol ratio of O to 2-methylimidazole is 1:1-1:20; in the step (2), the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:20-20:1.
Further, zn (NO 3 ) 2 .6H 2 The mass ratio of O to polyurethane sponge is 3:1, zn (NO 3 ) 2 .6H 2 The mol ratio of O to 2-methylimidazole is 1:16; in the step (2), the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:11.
Further, the high-temperature carbonization temperature in the step (3) is 300-1200 ℃, and the carbonization time is 1-10 h.
Further, the high-temperature carbonization temperature in the step (3) is 900 ℃, and the carbonization time is 3 hours.
Further, the polyurethane sponge is sequentially soaked in a mixed solution of dilute hydrochloric acid and absolute ethyl alcohol/acetone, then is washed by absolute ethyl alcohol and deionized water, and is dried to obtain the pure polyurethane sponge.
Further, the concentration of the dilute hydrochloric acid is 1mol/L, and the volume ratio of the absolute ethyl alcohol to the acetone in the absolute ethyl alcohol/acetone mixed solution is 1:1.
further, in the step (1), the vacuum baking temperature is 60 ℃ and the time is 12 hours; the volume ratio of the methanol to the water in the methanol/water mixed solution in the step (2) is 1:1.
According to the invention, the self-supporting nitrogen-doped carbon/ZnS flexible composite material prepared by the preparation method disclosed by any one of claims 1-8.
The invention relates to application of a self-supporting nitrogen-doped carbon/ZnS flexible composite material in a lithium ion battery anode material. The self-supporting nitrogen-doped carbon/ZnS flexible composite material has the characteristics of good flexibility, high conductivity, high specific capacity and the like when used as a lithium ion anode material, and is an ideal flexible electrode material
In order to improve the cycle stability of ZnS materials, the modification means adopted at present mainly include carbon coating, doping and preparing ZnS materials with nano structures. The carbon coating can improve the compatibility of the ZnS-based composite material with the electrolyte and can also improve the conductivity of the composite material. The nitrogen-doped carbon has excellent mechanical property and good conductivity, and the conductivity and electrochemical property of the composite material can be improved by compounding with ZnS material. The invention combines the advantages and disadvantages of ZnS, takes polyurethane sponge as a matrix, combines ZnS and polyurethane sponge, carries out high-temperature treatment, and utilizes the synergistic effect of the composite material, and the self-supporting flexible composite electrode is taken as a lithium ion battery cathode material, thereby hopefully improving the electrochemical performance of the lithium ion battery.
Advantageous effects
The raw materials for preparing the self-supporting nitrogen-doped carbon/ZnS flexible composite material are economical and environment-friendly, the preparation process is relatively simple, and the cost is low; the nitrogen-doped carbon porous material is formed after the polyurethane sponge is carbonized at a high temperature, the active site for lithium storage can be effectively improved by nitrogen doping, the capacity can be improved, the respective advantages of ZnS and nitrogen-doped carbon foam can be brought into play, and the conductivity and the cycling stability of ZnS can be effectively improved by the nitrogen-doped carbon foam prepared from the polyurethane sponge.
Drawings
FIG. 1 is a graph of the flexibility test of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 1;
FIG. 2 is a graph comparing the cycling performance of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 1 with that of pure ZnS.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without making any inventive effort are intended to fall within the scope of the present invention.
Example 1
(1) Purification of polyurethane sponge: the polyurethane sponge (the polyurethane sponge is soft foam sponge and is commercially purchased) is put into 1mol/L dilute hydrochloric acid to be soaked for 6 hours, then is transferred into a mixed solution of absolute ethyl alcohol/acetone (volume ratio is 1:1) to be soaked for 3 hours, is washed for 3 times by absolute ethyl alcohol and deionized water respectively, and is put into a drying box at 60 ℃ to be dried for 12 hours, so that the pure polyurethane sponge is obtained. (polyurethane sponge is a soft foam sponge, commercially available);
(2) Preparation of ZIF-8/polyurethane composite material: zn (NO) 3 ) 2 .6H 2 Dissolving O in methanol, adding into polyurethane sponge methanol dispersion, stirring for 30min, adding methanol-dissolved 2-methylimidazole, magnetically stirring at room temperature for reaction for 1h, washing the resultant with methanol for 3 times, and baking in a vacuum oven at 80deg.C for 12h to obtain ZIF-8/polyurethane composite material; zn (NO) 3 ) 2 6H2O and polyurethane sponge in a mass ratio of 3:1, zn (NO) 3 ) 2 .6H 2 The mol ratio of O to 2-methylimidazole is 1:16;
(3) Preparation of ZnS/polyurethane composite: adding the ZIF-8/polyurethane composite material prepared in the step (2) and thioacetamide into a methanol/water mixed solution (1:1), stirring for 30min under an argon atmosphere, then heating to 60 ℃ and stirring for 6h, washing the resultant with deionized water, and drying to obtain a ZnS/polyurethane composite material; the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:11;
(4) Preparation of self-supporting nitrogen-doped carbon/ZnS flexible composite: transferring the ZnS/polyurethane composite material prepared in the step (3) into a high-temperature tubular resistance furnace to carry out high-temperature carbonization under the nitrogen atmosphere, wherein the carbonization temperature is 900 ℃, the carbonization time is 3 hours, and cooling to obtain the ZnS/nitrogen-doped carbon foam composite material.
The flexibility of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 1 was tested, and the results are shown in fig. 1, and it can be seen from fig. 1 that the self-supporting nitrogen-doped carbon/ZnS flexible composite exhibited excellent mechanical flexibility.
The self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in the embodiment is used as a working electrode, a lithium sheet is used as a counter electrode, the electrolyte is a general lithium ion battery electrolyte, a 2032 button battery is prepared, the current density of 0.5A/g is used for charge and discharge, pure ZnS is used as a reference, the cycle performance curve is shown in fig. 2, it can be seen from fig. 2 that the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in the embodiment 1 can reach 707mAh/g for the first time, the discharge capacity after 100 cycles is 704mAh/g, the discharge capacity of pure ZnS is 810mAh/g for the first time, and the discharge capacity after 100 cycles is 190mAh/g.
Example 2
(1) The purification step of the polyurethane sponge is shown in the example step (1);
(2) Preparation of ZIF-8/polyurethane composite material: zn (NO) 3 ) 2 .6H 2 Dissolving O in methanol, adding into polyurethane sponge methanol dispersion, stirring for 30min, adding methanol-dissolved 2-methylimidazole, magnetically stirring at room temperature for reaction for 1h, washing the resultant with methanol for 3 times, and baking in a vacuum oven at 80deg.C for 12h to obtain ZIF-8/polyurethane composite material; zn (NO) 3 ) 2 6H2O to polyurethane sponge mass ratio 6:1, zn (NO) 3 ) 2 The molar ratio of 6H2O to 2-methylimidazole is 1:20;
(3) Preparation of ZnS/polyurethane composite: adding the ZIF-8/polyurethane composite material prepared in the step (2) and thioacetamide into a methanol/water mixed solution (1:1), stirring for 30min under an argon atmosphere, then heating to 60 ℃ and stirring for 6h, washing the resultant with deionized water, and drying to obtain a ZnS/polyurethane composite material; the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:20;
(4) Preparation of self-supporting nitrogen-doped carbon/ZnS flexible composite: transferring the ZnS/polyurethane composite material prepared in the step (3) into a high-temperature tubular resistance furnace to carry out high-temperature carbonization under the nitrogen atmosphere, wherein the carbonization temperature is 1200 ℃, the carbonization time is 10 hours, and cooling to obtain the ZnS/nitrogen-doped carbon foam composite material.
Taking example 1 as an example, the cycle performance of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 2 is tested, and the initial discharge capacity of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 2 can reach 701.5mAh/g at a current density of 0.5A/g, and the discharge capacity after 100 cycles is 456.8mAh/g.
Example 3
(1) The purification step of the polyurethane sponge is shown in the example step (1);
(2) Preparation of ZIF-8/polyurethane composite material: zn (NO) 3 ) 2 .6H 2 Dissolving O in methanolDissolving, adding into polyurethane sponge methanol dispersion, stirring for 30min, adding methanol-dissolved 2-methylimidazole, magnetically stirring at room temperature for reaction for 1h, washing the resultant with methanol for 3 times, and baking in a vacuum oven at 80deg.C for 12h to obtain ZIF-8/polyurethane composite material; zn (NO) 3 ) 2 6H2O to polyurethane sponge mass ratio of 10:1, zn (NO) 3 ) 2 The molar ratio of 6H2O to 2-methylimidazole is 1:1;
(3) Preparation of ZnS/polyurethane composite: adding the ZIF-8/polyurethane composite material prepared in the step (2) and thioacetamide into a methanol/water mixed solution (1:1), stirring for 30min under an argon atmosphere, then heating to 60 ℃ and stirring for 6h, washing the resultant with deionized water, and drying to obtain a ZnS/polyurethane composite material; the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:1;
(4) Preparation of self-supporting nitrogen-doped carbon/ZnS flexible composite: transferring the ZnS/polyurethane composite material prepared in the step (3) into a high-temperature tubular resistance furnace to carry out high-temperature carbonization under the nitrogen atmosphere, wherein the carbonization temperature is 300 ℃, the carbonization time is 1 hour, and cooling to obtain the ZnS/nitrogen-doped carbon foam composite material.
Taking example 1 as an example, the cycle performance of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 3 is tested, the initial discharge capacity of the self-supporting nitrogen-doped carbon/ZnS flexible composite prepared in example 2 can reach 527.8mAh/g at a current density of 0.5A/g, and the discharge capacity after 100 cycles is 366.9mAh/g.
Claims (10)
1. The preparation method of the self-supporting nitrogen-doped carbon/ZnS flexible composite material is characterized by comprising the following steps of:
(1) Preparation of ZIF-8/polyurethane composite material: dissolving zinc salt in methanol, adding the dissolved zinc salt into polyurethane sponge methanol dispersion liquid, stirring and mixing uniformly, adding 2-methylimidazole methanol solution, stirring and reacting at room temperature, washing a product with methanol, and baking in vacuum to obtain ZIF-8/polyurethane composite material;
(2) Preparation of ZnS/polyurethane composite: adding the ZIF-8/polyurethane composite material prepared in the step (1) and thioacetamide into a methanol/water mixed solution, uniformly stirring under an argon atmosphere, heating to 50-70 ℃, stirring for 4-10 hours, washing and drying to obtain a ZnS/polyurethane composite material;
(3) Preparation of self-supporting nitrogen-doped carbon/ZnS flexible composite: and (3) carbonizing the ZnS/polyurethane composite material prepared in the step (2) at a high temperature in a nitrogen atmosphere, and cooling to obtain the ZnS/nitrogen-doped carbon foam composite material.
2. The method for preparing a self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 1, wherein the zinc salt in step (1) is Zn (NO 3 ) 2 .6H 2 O，Zn(NO 3 ) 2 .6H 2 The mass ratio of O to polyurethane sponge is 1:10-10:1, zn (NO) 3 ) 2 .6H 2 The mol ratio of O to 2-methylimidazole is 1:1-1:20; in the step (2), the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:20-20:1.
3. The method for preparing a self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 1, wherein Zn (NO 3 ) 2 .6H 2 The mass ratio of O to polyurethane sponge is 3:1, zn (NO 3 ) 2 .6H 2 The mol ratio of O to 2-methylimidazole is 1:16; in the step (2), the molar ratio of the ZIF-8/polyurethane composite material to the thioacetamide is 1:11.
4. The method for preparing the self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 1, wherein the high-temperature carbonization temperature in the step (3) is 300-1200 ℃ and the carbonization time is 1-10 h.
5. The method for preparing a self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 1, wherein the high-temperature carbonization temperature in step (3) is 900 ℃ and the carbonization time is 3h.
6. The method for preparing the self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 1, wherein the polyurethane sponge is sequentially soaked in a mixed solution of dilute hydrochloric acid and absolute ethyl alcohol/acetone, then washed by absolute ethyl alcohol and deionized water, and dried to obtain the pure polyurethane sponge.
7. The method for preparing the self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 6, wherein the concentration of the dilute hydrochloric acid is 1mol/L, and the volume ratio of the absolute ethyl alcohol to the acetone in the absolute ethyl alcohol/acetone mixed solution is 1:1.
8. the method for preparing a self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 1, wherein the vacuum baking temperature in step (1) is 60 ℃ for 12 hours; the volume ratio of the methanol to the water in the methanol/water mixed solution in the step (2) is 1:1.
9. A self-supporting nitrogen-doped carbon/ZnS flexible composite prepared by the method of any one of claims 1 to 8.
10. Use of the self-supporting nitrogen-doped carbon/ZnS flexible composite according to claim 9 in a negative electrode material for a lithium ion battery.
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| CN111952572A (en) * | 2020-08-24 | 2020-11-17 | 洛阳理工学院 | Cobalt-nickel bimetallic nitrogen-doped carbon composite material containing single-atom active site and preparation method and application thereof |
| CN114284480A (en) * | 2021-12-23 | 2022-04-05 | 山东精工电子科技有限公司 | Nitrogen doped carbon/MoSe2/NiO/graphene flexible composite material, and preparation method and application thereof |
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| CN111952572A (en) * | 2020-08-24 | 2020-11-17 | 洛阳理工学院 | Cobalt-nickel bimetallic nitrogen-doped carbon composite material containing single-atom active site and preparation method and application thereof |
| CN114284480A (en) * | 2021-12-23 | 2022-04-05 | 山东精工电子科技有限公司 | Nitrogen doped carbon/MoSe2/NiO/graphene flexible composite material, and preparation method and application thereof |
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