CN115548283B - NiS (nickel-zinc sulfide)2Preparation method and application of @ C/HC electrode material - Google Patents
NiS (nickel-zinc sulfide)2Preparation method and application of @ C/HC electrode material Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 9
- BFCBTLZKYHVGEV-UHFFFAOYSA-N zinc nickel(2+) disulfide Chemical compound [S--].[S--].[Ni++].[Zn++] BFCBTLZKYHVGEV-UHFFFAOYSA-N 0.000 title 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 238000002360 preparation method Methods 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 238000011065 in-situ storage Methods 0.000 claims description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000011066 ex-situ storage Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 11
- 241000080590 Niso Species 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000861 blow drying Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 239000008121 dextrose Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- NKHCNALJONDGSY-UHFFFAOYSA-N nickel disulfide Chemical compound [Ni+2].[S-][S-] NKHCNALJONDGSY-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
-
- 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 a preparation method and application of NiS2@C/HC electrode material, wherein a solvent thermal method is adopted in the preparation method to prepare a nickel-based precursor Ni-BMZ, the nickel-based precursor Ni-BMZ is uniformly wrapped in a hydrothermal carbon layer (HC), and then the nickel-based precursor Ni-BMZ reacts with sulfur powder at high temperature to successfully prepare a NiS 2 @C/HC composite material. The preparation method of the invention does not need to add a surfactant or any template agent, greatly shortens the preparation period and has the characteristic of low-temperature synthesis. And exhibits excellent rate performance and cycle stability in aqueous secondary batteries. The preparation method successfully prepares NiS 2 @C/HC with a unique pea-shaped structure. When the NiS 2 @C/HC// TIP aqueous secondary battery is formed by matching with a Treated Iron Powder (TIP) electrode, the lithium ion battery has high discharge capacity, remarkable rate capability and good cycle stability.
Description
Technical Field
The invention relates to the technical field of synthesis of electrode materials of water-based secondary batteries, in particular to a preparation method and application of a NiS 2 @C/HC electrode material.
Background
With the massive consumption and exhaustion of traditional resources, renewable energy sources such as wind energy, solar energy and the like gradually draw attention. Because of the instability and intermittence of renewable energy sources, it is necessary to develop a wide range of energy storage systems. Among various energy storage systems, aqueous secondary batteries offer a difficult and expensive opportunity with the aim of achieving low cost, high safety, rapid ion migration, high capacity and long life. Despite their many of the above-noted advantages, their widespread use is limited by the large electrode volume expansion, structural deformation, and poor rate capability. In this case, it is urgent to design and prepare a composite electrode material having a suitable structure.
The metal sulfide generally has a high theoretical capacity and can be used as a candidate material for an aqueous secondary battery. To overcome the inherent drawbacks of carbon materials in terms of capacity, niS 2 operating in alkaline electrolytes is receiving increasing attention. However, nickel disulfide generally undergoes self-aggregation or volume expansion of nanoparticles during repeated charge and discharge, and electron and ion diffusion is retarded due to poor conductivity, resulting in lower discharge capacity, rate capability and cycle life. The traditional NiS 2 @C composite material is prepared by taking thiourea or sodium sulfide as a sulfur source and adopting an ex-situ carbon coating method, so that the preparation process is complex, time-consuming and unfriendly. How to synthesize the NiS 2 @C composite material by using a green efficient method has certain challenges, especially the combination of in-situ carbon coating and ex-situ carbon coating technologies.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method and application of a NiS 2 @C/HC electrode material. The preparation method adopts a solvothermal method to prepare a nickel-based precursor Ni-BMZ, uniformly wraps the nickel-based precursor Ni-BMZ in a hydrothermal carbon layer (HC), and then reacts with sulfur powder at high temperature to successfully prepare the NiS 2 @C/HC composite material. The preparation method of the invention does not need to add a surfactant or any template agent, greatly shortens the preparation period and has the characteristic of low-temperature synthesis. And exhibits excellent rate performance and cycle stability in aqueous secondary batteries.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method of NiS 2 @C/HC electrode material is characterized by comprising the following steps:
step 1: adding NiSO 4·6H2 O and benzimidazole with the mass ratio of 2:5-4:5 into a mixed solution of water and ethanol (with the volume ratio of 1:1), and magnetically stirring at a constant speed until the mixture is dissolved to obtain a mixture.
Step 2: then transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, placing 3-5 h in a blast drying box at 160-200 ℃, cooling to room temperature, and obtaining a green precursor (Ni-BMZ) by a centrifugal method.
Step 3: re-dispersing the green precursor into glucose aqueous solution of 0.03-0.07M, transferring into a reaction kettle, reacting at 110-130 ℃ for 3-5 h, and centrifuging to obtain the Ni-BMZ/HC composite material.
Step 4: mixing and grinding Ni-BMZ/HC composite material and sulfur powder with the mass ratio of 1:2-1:4 into uniform powder. Roasting the uniform powder in a tubular furnace at 480-520 ℃ under Ar atmosphere for 1-3 h, and obtaining the carbon with the in-situ carbon and ex-situ carbon ratio of 1:0.7 to 1:2.2 NiS 2 @C/HC electrode material.
The NiS 2 @C/HC electrode material obtained by the preparation method has a unique pea-shaped structure, can also be called as a bean shape, HC is equivalent to pea skin, and NiS 2 @C is equivalent to intermediate pea balls.
Further, the invention provides application of NiS 2 @C/HC electrode material, wherein the electrode material is applied to an assembled water-based secondary battery, a treated iron powder electrode is used as an anode, a single electrode NiS 2 @C/HC electrode is used as a cathode, glass fiber is used as a diaphragm, and a 6M KOH aqueous solution is used as electrolyte; assembling an anode and a cathode NiS 2 @C/HC into a double-electrode system; wherein the single electrode NiS 2 @C/HC electrode is obtained by the preparation method.
When the electrode material is applied to an aqueous secondary battery, the capacity retention rate of the aqueous secondary battery after the aqueous secondary battery is cycled 10000 times under the ultra-large current density of 15A g -1 is more than 74%, the discharge capacity of the aqueous secondary battery is more than 185mAh g -1 under the current density of 1A g -1, and the discharge capacity of the aqueous secondary battery is more than 154.0 mAh g -1 under the current density of 5A g -1.
Compared with the prior art, the invention has the following advantages:
(1) The invention provides a preparation method and application of a thin-layer hydrothermal carbon-coated core-shell structure (NiS 2 @C/HC) electrode material. The preparation method successfully prepares NiS 2 @C/HC with a unique pea-shaped structure. The porous carbon in the material provides space for volume expansion of the NiS 2 nano particles, prevents aggregation of the NiS 2 nano particles, and meanwhile, the outer HC layer is beneficial to improving conductivity, promoting electron transfer and improving the mechanical strength of the whole active material. When the NiS 2 @C/HC// TIP aqueous secondary battery is formed by matching with a Treated Iron Powder (TIP) electrode, the lithium ion battery has high discharge capacity, remarkable rate capability and good cycle stability.
(2) The preparation method adjusts the ratio of in-situ carbon to ex-situ carbon by adjusting the glucose concentration, and adjusts the performance of the electrode material by controlling the ratio of in-situ carbon to ex-situ carbon. Experiments show that the electrode material obtained by the preparation method can be effectively applied to an aqueous secondary battery, the capacity retention rate of the aqueous secondary battery is more than 74% after the aqueous secondary battery is cycled 10000 times under the ultra-large current density of 15A g -1, the discharge capacity of the aqueous secondary battery is more than 185mAh g -1 under the current density of 1A g -1, and the discharge capacity of the aqueous secondary battery is more than 154.0 mAh g -1 under the current density of 5A g -1.
Drawings
Fig. 1 (a) and (b) are scanning electron microscope images of the NiS 2 @ C/HC electrode material prepared in example 1 of the present invention. FIGS. 1 (C) and (d) are transmission electron microscope images of NiS 2 @C/HC electrode materials produced in example 1 of the present invention.
FIG. 2 is a schematic representation of a unique pea-like structure of the NiS 2 @C/HC electrode material prepared in the present invention.
FIG. 3 is a constant current charge-discharge curve of NiS 2 @C/HC electrode material prepared in example 1 of the present invention in an aqueous secondary battery.
FIG. 4 is a graph showing the rate performance of the NiS 2 @C/HC electrode material prepared in example 1 of the present invention in an aqueous secondary battery.
FIG. 5 is a long-cycle curve of the NiS 2 @C/HC electrode material prepared in example 1 of the present invention in an aqueous secondary battery.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration of the invention and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be to those skilled in the art in light of the foregoing disclosure.
The invention provides a preparation method of a NiS 2 @C/HC electrode material, which comprises the following steps:
Step 1: niSO 4·6H2 O and benzimidazole with the mass ratio of 2:5-4:5 are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: then transferring the mixture into a polytetrafluoroethylene high-pressure reaction kettle, placing 3-5 h in a blast drying box at 160-200 ℃, cooling to room temperature, and obtaining a green precursor (Ni-BMZ) by a centrifugal method.
Step 3: re-dispersing the green precursor into glucose aqueous solution of 0.03-0.07M, transferring into a reaction kettle, reacting at 110-130 ℃ for 3-5 h, and centrifuging to obtain the Ni-BMZ/HC composite material.
Step 4: mixing and grinding Ni-BMZ/HC composite material and sulfur powder with the mass ratio of 1:2-1:4 into uniform powder. Roasting the uniform powder in a tubular furnace at 480-520 ℃ under Ar atmosphere for 1-3 h to obtain the NiS 2 @C/HC electrode material.
Preferably, the amount ratio of NiSO 4·6H2 O to benzimidazole material is 3:5; the concentration of the glucose aqueous solution is 0.05M; the mass ratio of the Ni-BMZ/HC composite material to the sulfur powder is 1:3.
Setting the temperature of the blast drying oven to 180 ℃ in the step 2, and preserving the temperature for 4 hours at the temperature; in the step 3, the temperature of the blast drying box is set to 120 ℃, and the temperature is kept for 4 hours; in step 4, the tube furnace temperature was set at 500℃and incubated for 2 hours.
The carbon in the BMZ of step 2 in the present invention is in situ carbon, i.e. the carbon of NiS 2 @C/HC is in situ carbon. In the step 3, carbon formed by adding glucose solution is off-site carbon, namely/HC is off-site carbon. The molar ratio of in-situ carbon to ex-situ carbon in the NiS 2 @C/HC electrode material is 1:0.7 to 1:2.2.
The NiS 2 @C/HC electrode material obtained by the preparation method has a unique pea-shaped structure, can also be called as a bean shape, HC corresponds to pea skin, niS 2 @C corresponds to middle pea balls, and a plurality of pea balls are wrapped in the pea skin, and the structure is schematically shown in figure 2. The particle size of the NiS 2 in the NiS 2 @C/HC electrode material is 8-15nm.
Example 1: the embodiment provides a preparation method of NiS 2 @C/HC electrode material, which comprises the following steps:
step 1: 6 mmol NiSO 4·6H2 O and 10mmol benzimidazole are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: the mixture of step 1 was then transferred to a teflon autoclave, placed in a forced air drying oven at 180 ℃ for 4 h, cooled to room temperature and centrifuged to obtain the green precursor (Ni-BMZ).
Step 3: the green precursor was redispersed in 80 mL dextrose aqueous solution (0.05M) and transferred to a reaction kettle, reacted at 120 ℃ for 4 h, and centrifuged to obtain the Ni-BMZ/HC composite material.
Step 4: the Ni-BMZ/HC composite material and the sulfur powder were mixed and ground into a uniform powder in a mass ratio of 1:3. And roasting the uniform powder in a 500 ℃ tubular furnace under Ar atmosphere for 2h to obtain the NiS 2 @C/HC electrode material with the in-situ carbon to ex-situ carbon molar ratio of 1:1.5.
The NiS 2 @C/HC electrode material obtained in this example was assembled into an aqueous secondary battery and applied to: the treated iron powder electrode was used as an anode (the iron powder electrode was treated according to the previous report). The single electrode NiS 2 @C/HC electrode is the cathode. The glass fiber is a diaphragm, and the 6M KOH aqueous solution is electrolyte. Finally, the anode and cathode NiS 2 @C/HC were assembled into a bipolar system (typically using 2032 button cells). Testing in electrochemical workstations and battery testing systems. The aqueous secondary battery had a discharge capacity of 205.1 mAh g -1 at a current density of 1A g -1 and a discharge capacity of 176.4 mAh g -1 at a current density of 5A g -1. The capacity retention was 80.8% after 10000 cycles at an ultra-large current density of 15A g -1.
Example 2: the embodiment provides a preparation method and application of a NiS 2 @C/HC electrode material, wherein the preparation method comprises the following steps:
step 1: 6 mmol NiSO 4·6H2 O and 10mmol benzimidazole are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: the mixture was then transferred to a teflon autoclave, placed in a blow-dry oven at 180 ℃ for 4h a, cooled to room temperature and centrifuged to obtain the green precursor (Ni-BMZ).
Step 3: the green precursor was redispersed in 80 mL dextrose aqueous solution (0.03M) and transferred to a reaction kettle, reacted at 120 ℃ for 4 h, and centrifuged to obtain the Ni-BMZ/HC composite material.
Step 4: the Ni-BMZ/HC composite material and the sulfur powder were mixed and ground into a uniform powder in a mass ratio of 1:3. And roasting the uniform powder in a 500 ℃ tubular furnace under Ar atmosphere for 2h to obtain the NiS 2 @C/HC electrode material with the in-situ carbon to ex-situ carbon ratio of 1:0.7.
The NiS 2 @C/HC electrode material obtained in this example was assembled into an aqueous secondary battery and applied to: the treated iron powder electrode was used as an anode (the iron powder electrode was treated according to the previous report). The single electrode NiS 2 @C/HC electrode is the cathode. The glass fiber is a diaphragm, and the 6M KOH aqueous solution is electrolyte. Finally, the anode and cathode NiS 2 @C/HC were assembled into a bipolar system (typically using 2032 button cells). Testing in electrochemical workstations and battery testing systems. The aqueous secondary battery had a discharge capacity of 187. mAh.g -1 at a current density of 1A g -1 and a discharge capacity of 155. mAh.g -1 at a current density of 5A g -1. The capacity retention was 74.9% after 10000 cycles at an ultra-large current density of 15A g -1.
Example 3: the embodiment provides a preparation method and application of a NiS 2 @C/HC electrode material, wherein the preparation method comprises the following steps:
step 1: 6 mmol NiSO 4·6H2 O and 10mmol benzimidazole are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: the mixture was then transferred to a teflon autoclave, placed in a blow-dry oven at 180 ℃ for 4h a, cooled to room temperature and centrifuged to obtain the green precursor (Ni-BMZ).
Step 3: the green precursor was redispersed in 80 mL dextrose aqueous solution (0.04M) and transferred to a reaction kettle, reacted at 120 ℃ for 4 h, and centrifuged to obtain the Ni-BMZ/HC composite material.
Step 4: the Ni-BMZ/HC composite material and the sulfur powder were mixed and ground into a uniform powder in a mass ratio of 1:3. And roasting the uniform powder in a 500 ℃ tubular furnace under Ar atmosphere for 2h to obtain the NiS 2 @C/HC electrode material with the in-situ carbon to ex-situ carbon ratio of 1:1.1.
The NiS 2 @C/HC electrode material obtained in this example was assembled into an aqueous secondary battery and applied to: the treated iron powder electrode was used as an anode (the iron powder electrode was treated according to the previous report). The single electrode NiS 2 @C/HC electrode is the cathode. The glass fiber is a diaphragm, and the 6M KOH aqueous solution is electrolyte. Finally, the anode and cathode NiS 2 @C/HC were assembled into a bipolar system (typically using 2032 button cells). Testing in electrochemical workstations and battery testing systems. The aqueous secondary battery had a discharge capacity of 196.5 mAh g -1 at a current density of 1A g -1 and a discharge capacity of 168.1 mAh g -1 at a current density of 5A g -1. The capacity retention rate after 10000 cycles at an ultra-large current density of 15A g -1 was 77.2%.
Example 4: the embodiment provides a preparation method and application of a NiS 2 @C/HC electrode material, wherein the preparation method comprises the following steps:
step 1: 6 mmol NiSO 4·6H2 O and 10mmol benzimidazole are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: the mixture was then transferred to a teflon autoclave, placed in a blow-dry oven at 180 ℃ for 4h a, cooled to room temperature and centrifuged to obtain the green precursor (Ni-BMZ).
Step 3: the green precursor was redispersed in 80 mL dextrose aqueous solution (0.06M), transferred to a reaction kettle, reacted at 120 ℃ for 4 h, and centrifuged to obtain the Ni-BMZ/HC composite material.
Step 4: the Ni-BMZ/HC composite material and the sulfur powder were mixed and ground into a uniform powder in a mass ratio of 1:3. And roasting the uniform powder in a 500 ℃ tubular furnace under Ar atmosphere for 2h to obtain the NiS 2 @C/HC electrode material with the in-situ carbon to ex-situ carbon ratio of 1:1.8.
The NiS 2 @C/HC electrode material obtained in this example was assembled into an aqueous secondary battery and applied to: the treated iron powder electrode was used as an anode (the iron powder electrode was treated according to the previous report). The single electrode NiS 2 @C/HC electrode is the cathode. The glass fiber is a diaphragm, and the 6M KOH aqueous solution is electrolyte. Finally, the anode and cathode NiS 2 @C/HC were assembled into a bipolar system (typically using 2032 button cells). Testing in electrochemical workstations and battery testing systems. The aqueous secondary battery had a discharge capacity of 194. mAh g -1 at a current density of 1A g -1 and a discharge capacity of 166. mAh g -1 at a current density of 5A g -1. The capacity retention was 76.8% after 10000 cycles at an ultra-large current density of 15A g -1.
Example 5: the embodiment provides a preparation method and application of a NiS 2 @C/HC electrode material, wherein the preparation method comprises the following steps:
step 1: 6 mmol NiSO 4·6H2 O and 10mmol benzimidazole are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: the mixture was then transferred to a teflon autoclave, placed in a blow-dry oven at 180 ℃ for 4h a, cooled to room temperature and centrifuged to obtain the green precursor (Ni-BMZ).
Step 3: the green precursor was redispersed in 80 mL dextrose aqueous solution (0.07M) and transferred to a reaction kettle, reacted at 120 ℃ for 4 h, and centrifuged to obtain the Ni-BMZ/HC composite material.
Step 4: the Ni-BMZ/HC composite material and the sulfur powder were mixed and ground into a uniform powder in a mass ratio of 1:3. And roasting the uniform powder in a 500 ℃ tubular furnace under Ar atmosphere for 2 h hours to obtain the NiS 2 @C/HC electrode material with the in-situ carbon to ex-situ carbon ratio of 1:2.2.
The NiS 2 @C/HC electrode material obtained in this example was assembled into an aqueous secondary battery and applied to: the treated iron powder electrode was used as an anode (the iron powder electrode was treated according to the previous report). The single electrode NiS 2 @C/HC electrode is the cathode. The glass fiber is a diaphragm, and the 6M KOH aqueous solution is electrolyte. Finally, the anode and cathode NiS 2 @C/HC were assembled into a bipolar system (typically using 2032 button cells). Testing in electrochemical workstations and battery testing systems. The aqueous secondary battery had a discharge capacity of 185.4 mAh g -1 at a current density of 1A g -1 and a discharge capacity of 154.8 mAh g -1 at a current density of 5A g -1. The capacity retention was 74.5% after 10000 cycles at an ultra-large current density of 15A g -1.
Comparative example 1: the comparative example provides a preparation method and application of an electrode material, wherein the preparation method comprises the following steps:
step 1: 6 mmol NiSO 4·6H2 O and 10mmol benzimidazole are added into a mixed solution of water and ethanol (volume ratio is 1:1), and the mixture is magnetically stirred at a constant speed until the mixture is dissolved.
Step 2: the mixture was then transferred to a teflon autoclave, placed in a blow-dry oven at 180 ℃ for 4h a, cooled to room temperature and centrifuged to obtain the green precursor (Ni-BMZ).
Step 3: the green precursor was redispersed in 80 mL deionized water and transferred to a reaction kettle, reacted at 120 ℃ for 4: 4h and centrifuged.
Step 4: ni-BMZ and sulfur powder in a mass ratio of 1:3 were mixed and ground into a uniform powder. And roasting the uniform powder in a 500 ℃ tubular furnace under Ar atmosphere for 2h to obtain the NiS 2 @C electrode material without in-situ carbon.
The NiS 2 @C electrode material obtained in the comparative example was assembled into an aqueous secondary battery for application: the treated iron powder electrode was used as an anode (the iron powder electrode was treated according to the previous report). The single electrode NiS 2 @C electrode is used as a cathode. The glass fiber is a diaphragm, and the 6M KOH aqueous solution is electrolyte. Finally, the anode and cathode NiS 2 @ C were assembled into a bi-electrode system (typically using 2032 button cells). Testing in electrochemical workstations and battery testing systems. The aqueous secondary battery had a discharge capacity of 177.8 mAh g -1 at a current density of 1A g -1 and a discharge capacity of 139.0 mAh g -1 at a current density of 5A g -1. The capacity retention was 70.3% after 10000 cycles at an ultra-large current density of 15A g -1.
Fig. 1 (a) and (b) are scanning electron microscope images of the NiS 2 @ C/HC electrode material prepared in example 1 of the present invention. FIGS. 1 (C) and (d) are transmission electron microscope images of NiS 2 @C/HC electrode materials produced in example 1 of the present invention. The NiS 2 @C/HC hybrid material is uniformly distributed and shows a pea-shaped core-shell nano structure. The NiS 2 @ C nanoparticles have been covered with an HC layer of about 12 a nm a thick. In addition, lattice fringes were observed in the HRTEM image, with a corresponding lattice spacing of about 0.28 nm, which is the (200) plane of NiS 2.
The size of NiS 2 nano particles in the electrode material obtained by the preparation method is about 10nm, so that the diffusion distance of electrons and ions in the active material is reduced. The porous carbon in the interior provides space for volume expansion of the NiS 2 nano-particles, prevents aggregation of the NiS 2 nano-particles and ensures high-rate performance of the NiS 2 nano-particles. The HC layer on the surface is beneficial to improving the conductivity of the material, preventing agglomeration of NiS 2 @C nano particles, further improving the mechanical strength of the whole active material and ensuring the strong circulation stability of the active material.
The present embodiment has a large difference in performance in the aqueous secondary battery as compared with the comparative example. The NiS 2 @C/HC electrode material has higher discharge capacity under the same current density, and has excellent stability.
The above embodiments are merely illustrative of the principles and applications of the present invention, and are provided to facilitate understanding of the method and core ideas of the present invention; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. Accordingly, the description is not to be taken as limiting the invention.
The invention is applicable to the prior art where it is not described.
Claims (6)
1. A preparation method of NiS 2 @C/HC electrode material is characterized by comprising the following steps:
Step 1: adding NiSO 4·6H2 O and benzimidazole with the mass ratio of 2:5-4:5 into the mixture with the volume ratio of 1:1, in a mixed solution of water and ethanol, magnetically stirring at a constant speed until the mixed solution is completely dissolved to obtain a mixture;
Step 2: transferring the mixture into a high-pressure reaction kettle of polytetrafluoroethylene, placing 3-5 h in a blast drying oven at 160-200 ℃, cooling to room temperature, and obtaining a green precursor Ni-BMZ through a centrifugal method;
Step 3: re-dispersing the green precursor Ni-BMZ into a glucose aqueous solution of 0.03-0.07M, transferring into a reaction kettle, reacting at 110-130 ℃ for 3-5 h, and centrifuging to obtain a Ni-BMZ/HC composite material;
Step 4: mixing and grinding the Ni-BMZ/HC composite material and sulfur powder with the mass ratio of 1:2-1:4 into uniform powder, and roasting the uniform powder in a tubular furnace at 480-520 ℃ under Ar atmosphere for 1-3 h to obtain a NiS 2 @C/HC electrode material;
the NiS 2 @C/HC electrode material has a pea-like structure, wherein HC corresponds to pea skin and NiS 2 @C corresponds to intermediate pea balls.
2. The method for preparing the NiS 2 @C/HC electrode material according to claim 1, wherein the amount ratio of the NiSO 4·6H2 O to the benzimidazole substance is 3:5; the concentration of the glucose aqueous solution is 0.05M; the mass ratio of the Ni-BMZ/HC composite material to the sulfur powder is 1:3.
3. The method for producing a NiS 2 @c/HC electrode material according to claim 1, wherein the temperature of the blow drying oven in step 2 is set to 180 ℃, and the heat is preserved at this temperature for 4 hours; in the step 3, transferring the mixture into a reaction kettle, and reacting at 120 ℃ for 4 h; in step 4, the tube furnace temperature was set at 500℃and incubated for 2 hours.
4. The method for preparing the NiS 2 @C/HC electrode material according to claim 1, wherein the particle size of NiS 2 in the NiS 2 @C/HC electrode material is 8-15nm.
5. A NiS 2 @ C/HC electrode material, characterized in that it is obtained by a preparation method according to any one of claims 1-4, wherein the molar ratio of in-situ carbon to ex-situ carbon in the NiS 2 @ C/HC electrode material is 1:0.7 to 1:2.2, the carbon in the BMZ of the step 2 is in-situ carbon, and the carbon formed by adding the glucose solution in the step 3 is ex-situ carbon.
6. The application of the NiS 2 @C/HC electrode material according to claim 5, wherein the electrode material is applied to an assembled water-based secondary battery, a treated iron powder electrode is used as an anode, a single electrode NiS 2 @C/HC electrode is used as a cathode, glass fibers are used as a diaphragm, and a 6M KOH aqueous solution is used as an electrolyte; the anode and cathode are assembled into a bipolar system.
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