CN116646503A - Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery - Google Patents
Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery Download PDFInfo
- Publication number
- CN116646503A CN116646503A CN202310929193.8A CN202310929193A CN116646503A CN 116646503 A CN116646503 A CN 116646503A CN 202310929193 A CN202310929193 A CN 202310929193A CN 116646503 A CN116646503 A CN 116646503A
- Authority
- CN
- China
- Prior art keywords
- ball
- milling
- transition metal
- carbon
- mnte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 64
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 36
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 173
- 229910017231 MnTe Inorganic materials 0.000 claims abstract description 66
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 62
- 239000002131 composite material Substances 0.000 claims abstract description 50
- 239000011324 bead Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000010405 anode material Substances 0.000 claims abstract description 8
- 239000007774 positive electrode material Substances 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 5
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims abstract description 3
- NZIHMSYSZRFUQJ-UHFFFAOYSA-N 6-chloro-1h-benzimidazole-2-carboxylic acid Chemical compound C1=C(Cl)C=C2NC(C(=O)O)=NC2=C1 NZIHMSYSZRFUQJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 3
- VMINMXIEZOMBRH-UHFFFAOYSA-N manganese(ii) telluride Chemical compound [Te]=[Mn] VMINMXIEZOMBRH-UHFFFAOYSA-N 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 23
- 230000002441 reversible effect Effects 0.000 claims description 15
- 239000004570 mortar (masonry) Substances 0.000 claims description 7
- 238000009825 accumulation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 239000011572 manganese Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000000713 high-energy ball milling Methods 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004771 selenides Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a carbon-coated transition metal telluride and application thereof in a water-based zinc ion battery, wherein the preparation process comprises the following steps: grinding and mixing a commercial transition metal telluride and a conductive carbon source, transferring the mixed material into a ball milling tank filled with ball milling beads, and performing ball milling and mixing by using a planetary ball mill to obtain a carbon-coated transition metal telluride which is used as an anode material of the water-based zinc ion battery to improve the multiplying power performance and the cycle stability performance of the water-based zinc ion battery, wherein the transition metal telluride is one or more of manganese telluride, nickel telluride, cadmium telluride or bismuth telluride, and the conductive carbon source is a carbon nano tube. The MnTe@CNTs composite material prepared by the method has excellent specific capacity, structural stability and conductivity, and when being used as a water-based zinc ion battery positive electrode material, the MnTe@CNTs composite material has good multiplying power performance and circulation stability performance.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a preparation method of a carbon-coated transition metal telluride and application of the carbon-coated transition metal telluride in a water-based zinc ion battery.
Background
Electrochemical energy storage technology has important significance for conversion and reserve of natural resources, and especially development of high-safety and low-cost electric energy storage technology is a key way for realizing sustainable development in the future. Among the various types of secondary energy batteries, aqueous zinc ion batteries (Aqueous zinc ion batteries, AZIBs) are considered as an emerging secondary energy battery, and are considered as powerful candidates for large-scale energy storage technologies due to their high energy density, high abundance, low cost, simple assembly process, use of safer aqueous solutions as electrolytes, and high ionic conductivity.
In various water-based zinc ion battery anode materials, the anode materials are mixed with vanadium-based compounds, prussian blue analogues and polyanionsCompared with the anode materials such as ionic compounds, the manganese-based compounds have the advantages of low cost, low toxicity, multiple types, high voltage platform, high theoretical specific capacity and the like, and are widely researched by scientific researchers. The transition metal element manganese (Mn) is widely present in nature because it has a variety of oxidation states (Mn 0 、Mn 2+ 、Mn 3+ 、Mn 4+ 、Mn 7+ ) There are various types of manganese-based compounds, and the manganese-based compounds are abundant in structure, so that redox characteristics are increased, and energy storage mechanisms of different substances are obviously different, so that the manganese-based compounds are considered as energy storage materials with great development prospects.
At present, researches on sulfides and selenides in chalcogenides are mature, but lower conductivity limits electron transportation in the electrochemical reaction process, tellurium elements in the same main group as sulfur and selenium are strong in metal, and telluride formed with transition metals also shows metal and is expected to become a novel electrochemical electrode material. When used as a positive electrode material of an aqueous zinc ion battery, the transition metal telluride has high conductivity and high theoretical volume capacity. In addition, the transition metal telluride is a typical layered material, has larger interlayer spacing, is favorable for rapid transmission of ions between layers, and shows good ion storage capacity and rapid diffusion power, but the commercialized telluride material has larger particles, prevents electron transmission, prevents the exertion of electrochemical performance, and directly leads to poor cycle stability performance and rate performance.
In order to improve the electrochemical performance, an effective method is to use carbon nanotubes with high conductivity to be mixed with commercial telluride materials by high-energy ball milling to obtain carbon-coated composite materials. The high-energy ball milling not only can reduce the particle size of the material, but also can lead the material to be more fully compounded with the carbon nano tubes, and the reason for selecting the Carbon Nano Tubes (CNTs) as the coating layer is as follows: (1) The carbon nano tube is a one-dimensional nano material, has a special structure and has a larger specific surface area; (2) The carbon nano tube with special structure and property has wide application in the energy storage field, and excellent electronic conductivity not only improves the conductivity of the electrode material and accelerates the transmission of ions, but also shortens the transmission distance of the ions and realizes faster reaction kinetics; (3) The carbon nano tube has hydrophobicity and is wrapped outside the manganese-based compound, so that the dissolution of the manganese-based compound can be effectively inhibited, the interface is stabilized, and the rate performance of the carbon nano tube is improved. However, there is currently no report on the selection of CNTs and commercial transition metal telluride and the preparation of carbon coated transition metal telluride by high energy ball milling.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of carbon-coated transition metal telluride with simple process, economy, environmental protection and good reproducibility, wherein the high-energy ball milling method utilizes the adaptation of different ball milling bead sizes and proportions to precisely control the particle size of ball milling particles, thereby being beneficial to the diffusion of ions between layers. Under certain ball-milling time and rotational speed, when ball-milling ball quantity is too much, more energy is generated during rotation, the structure of the material can be damaged, the electrochemical performance of the material is influenced, and when the ball-milling ball quantity is too little, the material cannot be ground into proper particle size, the transmission of ions is not facilitated, so that the ball-material ratio of the ball-milling is extremely important to precisely control. The carbon nano tube is used as a medium for electron transmission, so that the conductivity of the active material is improved, the carbon nano tube is wrapped on the outer surface of the active material, the direct contact between the active material and electrolyte is avoided, and the dissolution of the manganese-based compound can be effectively inhibited. When the carbon-coated transition metal telluride prepared by the method is used for a water-based zinc ion battery anode material, the carbon-coated transition metal telluride has relatively excellent rate capability and cycle stability.
The invention adopts the following technical scheme to solve the technical problems, and is characterized by comprising the following specific steps: grinding and mixing a commercial transition metal telluride and a conductive carbon source, transferring the mixed material into a ball milling tank filled with ball milling beads, and performing ball milling and mixing by using a planetary ball mill to obtain a carbon-coated transition metal telluride which is used as an anode material of the water-based zinc ion battery to improve the multiplying power performance and the cycle stability performance of the water-based zinc ion battery, wherein the transition metal telluride is one or more of manganese telluride, nickel telluride, cadmium telluride or bismuth telluride, and the conductive carbon source is a carbon nano tube.
Further limited, the ball-milling balls in the ball-milling tank are agate ball-milling balls with the diameter of 4mm, agate ball-milling balls with the diameter of 8mm and agate ball-milling balls with the diameter of 10mm, wherein the agate ball-milling balls with the diameter of 4mm account for 15-30% of the total ball-milling balls, the agate ball-milling balls with the diameter of 8mm account for 40-70% of the total ball-milling balls, and the agate ball-milling balls with the diameter of 10mm account for 15-30% of the total ball-milling balls.
Further limiting, the ball milling mixing process adopts 200-600r/min rotating speed to intermittently and alternately perform forward and reverse ball milling for 4-12h, the intermittent and alternate forward and reverse ball milling process is that forward ball milling is performed for 5min, then intermittent stop is performed for 1min, reverse ball milling is performed for 5min, and the process is repeated until the ball milling accumulation time is equal to the set ball milling time, wherein the intermediate intermittent time does not count the total ball milling time.
Further defined, the carbon-coated transition metal telluride is specifically a MnTe@CNTs composite material, and the specific preparation process of the MnTe@CNTs composite material comprises the following steps: grinding 100-194mg of commercial MnTe material and 6-100mg of CNTs in a mortar for 20-40min, transferring the mixture into a ball milling tank filled with 20-50g of ball milling beads for mixing, ball milling and mixing by using a planetary ball mill, and ball milling for 4-12h at a rotating speed of 200-600r/min to obtain the MnTe@CNTs composite material.
Further defined, a layer of carbon nano tube is uniformly wrapped on the surface of the commercialized MnTe@CNTs composite material to form the MnTe@CNTs composite material, wherein the mass percentage of the commercialized MnTe material in the MnTe@CNTs composite material is 50% -97%, and the balance is the carbon nano tube.
Further defined, the mass percentage of the commercial MnTe material in the MnTe@CNTs composite material is 80%, and the mass percentage of the commercial MnTe material in the MnTe@CNTs composite material is 20%.
Further limited, the ball-milling balls in the ball-milling tank are agate ball-milling balls with the diameter of 4mm, agate ball-milling balls with the diameter of 8mm and agate ball-milling balls with the diameter of 10mm, wherein the agate ball-milling balls with the diameter of 4mm account for 20% of the total ball-milling balls, the agate ball-milling balls with the diameter of 8mm account for 60% of the total ball-milling balls, and the agate ball-milling balls with the diameter of 10mm account for 20% of the total ball-milling balls.
The application of the carbon-coated transition metal telluride in the anode material of the water-based zinc ion battery is provided.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the preparation method has the advantages of simple preparation process, low cost, environmental protection and safety, and is expected to be used for industrial production.
2. The carbon atoms in the carbon nano tube adopt sp 2 The hybridization is connected with three nearest carbon atoms to form a compact structure, so that electrons with large pi bonds are highly delocalized on the whole side wall, and therefore, the high zinc storage kinetics of the MnTe@CNTs composite material in the charge and discharge process is improved, and excellent electrochemical performance is obtained. The excellent electrochemical performance is derived from the special structure and property of the MnTe@CNTs composite material, and the carbon nano tube is of a hollow tubular structure, has higher specific surface area and excellent electron conductivity, is used as a medium for electron transmission in the charge and discharge process, not only improves the conductivity of the electrode material, accelerates the ion diffusion and transfer, but also shortens the ion transmission distance.
3. The planetary ball mill provided by the invention drives ball milling balls to collide by using the rotation of the tank body, so that the size of solid particles is reduced. In the ball milling process, agate ball milling beads with larger diameters are heavier, more energy is generated by collision with the inner wall of a ball milling tank, but some collision dead angles exist. The agate ball-milling beads with smaller diameter are lighter, and the smaller the energy generated by collision with the inner wall of the ball-milling tank is, the more suitable for the particle refinement process. On one hand, through adding the agate ball-milling beads with different diameters, the ball-milling process is finer, the diameter of ball-milling particles is precisely controlled, and more reaction points can be provided for materials. On the other hand, under certain ball milling time and rotating speed, the ball milling process utilizes ball milling beads with different diameters and different proportions to carry out adaptation, thereby being beneficial to the diffusion of ions between layers. Because the ball-milling beads are too much in quantity, the structure of the material can be damaged, the electrochemical performance of the material is affected, and the ball-milling beads are too little in quantity, the material cannot be ground into proper particle size, and the ion transmission is not facilitated, so that the precise control of the ball-milling ball-material ratio is extremely important.
4. CNTs adopted in the preparation process of the invention are very easy to be compounded with and coated on the surface of the commercial MnTe material. If the conductive carbon source is changed, a highly conductive composite material will not be obtained, while having poor electrochemical properties. CNTs have hydrophobicity and are coated on the surface of a commercial MnTe material, so that the direct contact between an active material and electrolyte is avoided, and the dissolution of manganese ions can be effectively inhibited, so that the structural integrity of the composite material is ensured in the charge-discharge process, the prepared MnTe@CNTs composite material has good multiplying power performance and circulation stability performance, and the problems of excessively rapid capacity attenuation, poor circulation stability and the like of a manganese-based compound positive electrode material are fundamentally solved.
5. The commercialized MnTe material is a layered compound with larger interlayer spacing, high specific capacity and multiple charge and discharge platforms, and has good zinc storage performance. The invention adopts commercial MnTe material, and obtains the MnTe@CNTs composite material with excellent multiplying power performance and good cycle stability by carrying out high-energy ball milling and mixing with CNTs under certain conditions. After ball milling, the obtained MnTe@CNTs composite material has smaller particles and larger specific surface area, is favorable for infiltration of electrolyte, and ensures that the deintercalation of zinc ions has quick reaction kinetics.
Drawings
FIG. 1 is a scanning electron microscope image of the MnTe@CNTs composite material prepared in example 1.
FIG. 2 is an X-ray powder diffraction pattern of a commercial MnTe@CNTs composite material prepared in example 1, and CNTs.
FIG. 3 is a graph showing the rate performance of the MnTe@CNTs composite material prepared in example 1 and comparative examples 1-4 as a positive electrode material of a water-based zinc-ion battery.
FIG. 4 shows that the MnTe@CNTs composite material prepared in example 1 and comparative examples 1-4 has a current density of 5A g as a positive electrode material of a water-based zinc-ion battery -1 Graph of cyclic performance at that time.
Detailed Description
The above-described matters of the present invention will be described in further detail by way of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the following examples, and all techniques realized based on the above-described matters of the present invention are within the scope of the present invention.
Examples
Preparation of MnTe@CNTs composite material
160mg of commercial MnTe material and 40mg of CNTs are ground for 20min in a mortar, then the materials are transferred to a ball milling tank filled with 30g of ball milling balls for ball milling mixing by using a planetary ball mill, the ball milling balls in the ball milling tank are agate ball milling balls with the diameter of 4mm, agate ball milling balls with the diameter of 8mm and agate ball milling balls with the diameter of 10mm, wherein the agate ball milling balls with the diameter of 4mm account for 20% of the total ball milling balls, the agate ball milling balls with the diameter of 8mm account for 20% of the total ball milling balls, the ball milling balls with the diameter of 10mm account for 20% of the total ball milling balls, the ball milling is intermittently and alternately performed for 6h at the rotating speed of 500r/min, the ball milling process is intermittently stopped for 1min after the ball milling balls are alternately performed, the ball milling is continuously performed for reverse milling for 5min again, and the ball milling is repeatedly performed until the accumulated time is equal to the set ball milling time, wherein the intermediate batch time does not count the total ball milling time, and finally the MnTe CNTs composite material (marked as MnTe@CNTs) is obtained.
Comparative example 1
Preparation of MnTe@acetylene black composite material
160mg of commercial MnTe material and 40mg of acetylene black are ground for 20min in a mortar, then the materials are transferred to a ball milling tank filled with 30g of ball milling beads for ball milling mixing by using a planetary ball mill, the ball milling beads in the ball milling tank are agate ball milling beads with the diameter of 4mm, agate ball milling beads with the diameter of 8mm and agate ball milling beads with the diameter of 10mm, wherein the agate ball milling beads with the diameter of 4mm account for 20% of the total ball milling beads, the agate ball milling beads with the diameter of 8mm account for 20% of the total ball milling beads, the ball milling beads with the diameter of 10mm account for 20% of the total ball milling beads are intermittently and alternately subjected to forward and reverse ball milling for 6h at the rotating speed of 500r/min, the intermittent and alternate ball milling process is that the forward and reverse ball milling is intermittently stopped for 1min again, and the reverse ball milling is continuously performed for 5min, and the process is repeated until the cumulative time of ball milling is equal to the set ball milling time, wherein the intermediate batch time does not count the total ball milling time, and finally the MnTe@acetylene black composite material (marked as MnTe@black) is obtained.
Comparative example 2
Preparation of MnTe@Superp composite material
160mg of commercial MnTe material and 40mg of Superp are ground for 20min in a mortar, then the materials are transferred to a ball milling tank filled with 30g of ball milling balls for ball milling mixing by using a planetary ball mill, agate ball milling balls with the diameter of 4mm, agate ball milling balls with the diameter of 8mm and agate ball milling balls with the diameter of 10mm are selected as the ball milling balls in the ball milling tank, wherein the agate ball milling balls with the diameter of 4mm account for 20% of the total ball milling balls, the agate ball milling balls with the diameter of 8mm account for 20% of the total ball milling balls, the agate ball milling balls with the diameter of 10mm account for 20% of the total ball milling balls, the ball milling is intermittently and alternately performed for 6h at the rotating speed of 500r/min, the intermittent alternating positive and negative ball milling process is intermittently stopped for 1min and then the reverse ball milling is continued for 5min, and the process is repeated until the ball milling accumulation time is equal to the set time, wherein the intermediate batch time does not count the total ball milling time, and finally the MnTe Superp composite material (marked as MnTe@SuperTe) is obtained.
Comparative example 3
160mg of commercial MnTe material and 40mg of CNTs were ground in a mortar for 20 minutes to obtain a MnTe@CNTs composite material (labeled as non ball-mill).
Comparative example 4
160mg of commercial MnTe material and 40mg of CNTs are ground for 20min in a mortar, then the materials are transferred into a ball milling tank filled with 30g of ball milling beads for ball milling mixing by using a planetary ball mill, agate ball milling beads with the diameter of 10mm are selected as the ball milling beads in the ball milling tank, the ball milling is intermittently and alternately carried out for 6h in a forward and reverse rotation mode at the rotating speed of 500r/min, the intermittent and alternate forward and reverse rotation ball milling process is carried out for 5min, then the intermittent and reverse rotation ball milling is carried out for 5min, the process is repeated until the accumulated time of ball milling is equal to the set ball milling time, the total ball milling time is not counted in the middle intermittent time, and finally the MnTe@CNTs composite material (marked as 10mm diameter) is obtained.
The MnTe@CNTs composite material prepared in example 1 was characterized by SEM, as shown in FIG. 1. FIG. 2 shows XRD patterns of commercial MnTe@CNTs, and the MnTe@CNTs composite material prepared in example 1, wherein the MnTe@CNTs composite material prepared in example 1 contains carbon nanotubes, and no chemical change occurs before and after ball milling, so that no other diffraction peak occurs.
The MnTe@CNTs composite material prepared in example 1, conductive Carbon Sources (CNTs) and a binder (PVDF) are mixed according to the mass ratio of 70:20:10 to prepare fine slurry, the fine slurry is uniformly coated on a stainless steel mesh current collector to obtain a working electrode, zinc metal is used as a counter electrode, a glass fiber microporous filter membrane (Whatman company in UK) GF/D is used as a diaphragm, and 3mol L of the working electrode is prepared - 1 ZnSO 4 +0.2mol L -1 MnSO 4 As an electrolyte, a battery was assembled in air. And (3) carrying out charge and discharge test on the assembled battery on a new Wei charge and discharge tester, wherein the charge and discharge interval of the test is 0.2-1.6V. At 0.1A g -1 、0.3A g -1 、0.5A g -1 、1A g -1 、3A g -1 、5A g -1 The rate performance of the assembled battery was tested at a charge-discharge rate of 5A g -1 The cycle performance of the assembled battery was tested at the rate of (2). As can be seen from FIG. 3, the MnTe@CNTs composite material prepared in example 1 is in a range of 0.1. 0.1A g -1 Under the current density, the first reversible specific capacity reaches 501mA h g -1 The MnTe@CNTs composite material prepared in comparative examples 1-4 has rate capability inferior to that of the MnTe@CNTs composite material prepared in example 1. As can be seen from FIG. 4, the MnTe@CNTs composite material prepared in example 1 is found in 5A g -1 The specific capacity of the drop point under the condition is 210mA h g -1 With the increase of the cycle times, the specific discharge capacity tends to increase, and the discharge capacity can still be maintained at 195mA h g after 100 cycles -1 The capacity retention rate can still reach 92.86%, and the cycle stability of the MnTe@CNTs composite material prepared by comparative examples 1-4 is lower than that of the MnTe@CNTs composite material prepared by example 1. The MnTe@CNTs composite material prepared in the example 1 is shown to have excellent rate capability and cycle stability performance when being used as a positive electrode material of a water-based zinc ion battery.
While the basic principles, principal features and advantages of the present invention have been described in the foregoing examples, it will be appreciated by those skilled in the art that the present invention is not limited by the foregoing examples, but is merely illustrative of the principles of the invention, and various changes and modifications can be made without departing from the scope of the invention, which is defined by the appended claims.
Claims (8)
1. The preparation method of the carbon-coated transition metal telluride is characterized by comprising the following specific steps of: grinding and mixing a commercial transition metal telluride and a conductive carbon source, transferring the mixed material into a ball milling tank filled with ball milling beads, and performing ball milling and mixing by using a planetary ball mill to obtain a carbon-coated transition metal telluride which is used as an anode material of the water-based zinc ion battery to improve the multiplying power performance and the cycle stability performance of the water-based zinc ion battery, wherein the transition metal telluride is one or more of manganese telluride, nickel telluride, cadmium telluride or bismuth telluride, and the conductive carbon source is a carbon nano tube.
2. The method for producing a carbon-coated transition metal telluride according to claim 1, characterized in that: the ball-milling beads in the ball-milling tank are agate ball-milling beads with the diameter of 4mm, agate ball-milling beads with the diameter of 8mm and agate ball-milling beads with the diameter of 10mm, wherein the agate ball-milling beads with the diameter of 4mm account for 15-30% of the total ball-milling beads, the agate ball-milling beads with the diameter of 8mm account for 40-70% of the total ball-milling beads, and the agate ball-milling beads with the diameter of 10mm account for 15-30% of the total ball-milling beads.
3. The method for producing a carbon-coated transition metal telluride according to claim 1, characterized in that: the ball milling mixing process adopts 200-600r/min rotating speed to intermittently and alternately perform forward and reverse ball milling for 4-12h, the intermittent and alternate forward and reverse ball milling process is that the forward ball milling is stopped intermittently for 1min after 5min, then reverse ball milling is continued for 5min, and the process is repeated until the ball milling accumulation time is equal to the set ball milling time, wherein the intermediate intermittent time does not count the total ball milling time.
4. The method for producing a carbon-coated transition metal telluride according to claim 1, characterized in that: the carbon-coated transition metal telluride is specifically a MnTe@CNTs composite material, and the preparation process of the MnTe@CNTs composite material comprises the following steps: grinding 100-194mg of commercial MnTe material and 6-100mg of CNTs in a mortar for 20-40min, transferring the mixture into a ball milling tank filled with 20-50g of ball milling beads for mixing, ball milling and mixing by using a planetary ball mill, and ball milling for 4-12h at a rotating speed of 200-600r/min to obtain the MnTe@CNTs composite material.
5. The method for producing a carbon-coated transition metal telluride according to claim 4, wherein: a layer of carbon nano tube is uniformly wrapped on the surface of the commercialized MnTe@CNTs composite material to form the MnTe@CNTs composite material, wherein the mass percentage of the commercialized MnTe@CNTs composite material is 50% -97%, and the balance is the carbon nano tube.
6. The method for producing a carbon-coated transition metal telluride according to claim 4, wherein: the commercial MnTe material in the MnTe@CNTs composite material accounts for 80% of the mass of the MnTe@CNTs composite material, and the mass of the CNTs accounts for 20% of the mass of the MnTe@CNTs composite material.
7. The method for producing a carbon-coated transition metal telluride according to claim 4, wherein: the ball-milling beads in the ball-milling tank are agate ball-milling beads with the diameter of 4mm, agate ball-milling beads with the diameter of 8mm and agate ball-milling beads with the diameter of 10mm, wherein the agate ball-milling beads with the diameter of 4mm account for 20% of the total ball-milling beads, the agate ball-milling beads with the diameter of 8mm account for 60% of the total ball-milling beads and the agate ball-milling beads with the diameter of 10mm account for 20% of the total ball-milling beads.
8. Use of a carbon-coated transition metal telluride prepared according to any one of claims 1-7 in an aqueous zinc ion battery positive electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310929193.8A CN116646503B (en) | 2023-07-27 | 2023-07-27 | Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310929193.8A CN116646503B (en) | 2023-07-27 | 2023-07-27 | Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116646503A true CN116646503A (en) | 2023-08-25 |
| CN116646503B CN116646503B (en) | 2024-08-23 |
Family
ID=87643758
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310929193.8A Active CN116646503B (en) | 2023-07-27 | 2023-07-27 | Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116646503B (en) |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180097166A (en) * | 2017-02-22 | 2018-08-30 | 가천대학교 산학협력단 | Transtion metaldichalcogenide-carbon nanocomposites and method for manufacturing the same |
| CN108807910A (en) * | 2018-06-13 | 2018-11-13 | 深圳市寒暑科技新能源有限公司 | A kind of water system Zinc ion battery |
| CN109420551A (en) * | 2017-08-22 | 2019-03-05 | 苏州宝时得电动工具有限公司 | Positive electrode and preparation method thereof, the battery comprising the positive electrode |
| CN109650348A (en) * | 2018-12-18 | 2019-04-19 | 深圳先进技术研究院 | Transition metal chalcogenide nanoscale twins material and preparation method thereof, cell negative electrode material, secondary cell and its application |
| CN110697664A (en) * | 2019-11-27 | 2020-01-17 | 南京邮电大学 | Transition metal chalcogenide nanodot and preparation method thereof |
| CN110828800A (en) * | 2019-10-31 | 2020-02-21 | 北京科技大学 | Aqueous zinc ion battery and preparation method of anode material thereof |
| KR20200063642A (en) * | 2018-11-28 | 2020-06-05 | 순천향대학교 산학협력단 | Secondary battery and manufacturing method using Prussian blue powder as cathode active material |
| KR102162418B1 (en) * | 2019-06-24 | 2020-10-06 | 울산과학기술원 | Chalcogenide compound-based solar absorber and manufacturing method thereof |
| CN112234189A (en) * | 2020-10-13 | 2021-01-15 | 深圳大学 | Tin telluride-based electrode material, preparation method thereof and lithium ion battery |
| US20210036331A1 (en) * | 2018-02-19 | 2021-02-04 | Arkema France | Active material formulation for li-s battery and preparation process |
| CN112758919A (en) * | 2020-12-28 | 2021-05-07 | 西安交通大学 | Nitrogen and sulfur double-doped graphene, preparation method thereof and method for preparing supercapacitor material by using same |
| CN113371759A (en) * | 2021-08-13 | 2021-09-10 | 河南师范大学 | Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material |
| WO2022001681A1 (en) * | 2020-06-28 | 2022-01-06 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method for iron sulfide composite positive electrode material of sulfide all-solid-state battery |
| CN115472803A (en) * | 2022-10-18 | 2022-12-13 | 山东石油化工学院 | Preparation method of TMDS-based zinc ion battery positive electrode material |
| CN115692669A (en) * | 2022-11-17 | 2023-02-03 | 华中科技大学 | Embedded conversion dual-mechanism heterogeneous interface material, preparation method and application |
-
2023
- 2023-07-27 CN CN202310929193.8A patent/CN116646503B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180097166A (en) * | 2017-02-22 | 2018-08-30 | 가천대학교 산학협력단 | Transtion metaldichalcogenide-carbon nanocomposites and method for manufacturing the same |
| CN109420551A (en) * | 2017-08-22 | 2019-03-05 | 苏州宝时得电动工具有限公司 | Positive electrode and preparation method thereof, the battery comprising the positive electrode |
| US20210036331A1 (en) * | 2018-02-19 | 2021-02-04 | Arkema France | Active material formulation for li-s battery and preparation process |
| CN108807910A (en) * | 2018-06-13 | 2018-11-13 | 深圳市寒暑科技新能源有限公司 | A kind of water system Zinc ion battery |
| KR20200063642A (en) * | 2018-11-28 | 2020-06-05 | 순천향대학교 산학협력단 | Secondary battery and manufacturing method using Prussian blue powder as cathode active material |
| CN109650348A (en) * | 2018-12-18 | 2019-04-19 | 深圳先进技术研究院 | Transition metal chalcogenide nanoscale twins material and preparation method thereof, cell negative electrode material, secondary cell and its application |
| KR102162418B1 (en) * | 2019-06-24 | 2020-10-06 | 울산과학기술원 | Chalcogenide compound-based solar absorber and manufacturing method thereof |
| CN110828800A (en) * | 2019-10-31 | 2020-02-21 | 北京科技大学 | Aqueous zinc ion battery and preparation method of anode material thereof |
| CN110697664A (en) * | 2019-11-27 | 2020-01-17 | 南京邮电大学 | Transition metal chalcogenide nanodot and preparation method thereof |
| WO2022001681A1 (en) * | 2020-06-28 | 2022-01-06 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method for iron sulfide composite positive electrode material of sulfide all-solid-state battery |
| CN112234189A (en) * | 2020-10-13 | 2021-01-15 | 深圳大学 | Tin telluride-based electrode material, preparation method thereof and lithium ion battery |
| CN112758919A (en) * | 2020-12-28 | 2021-05-07 | 西安交通大学 | Nitrogen and sulfur double-doped graphene, preparation method thereof and method for preparing supercapacitor material by using same |
| CN113371759A (en) * | 2021-08-13 | 2021-09-10 | 河南师范大学 | Preparation method and application of amorphous transition metal oxide packaged manganese-based oxide composite material |
| CN115472803A (en) * | 2022-10-18 | 2022-12-13 | 山东石油化工学院 | Preparation method of TMDS-based zinc ion battery positive electrode material |
| CN115692669A (en) * | 2022-11-17 | 2023-02-03 | 华中科技大学 | Embedded conversion dual-mechanism heterogeneous interface material, preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| LEE S;CHOI H;EOM K: "Enhancing the electrochemical performances of a tellurium-based cathode for a high-volumetric capacity Li battery via a high-energy ball mill with sulfur edge-functionalized carbon", 《JOURNAL OF POWER SOURCES》, vol. 430, 16 May 2019 (2019-05-16), pages 112 - 119 * |
| SEUNGMIN LEE 等: "Enhancing the electrochemical performances of a tellurium-based cathode for a high-volumetric capacity Li battery via a high-energy ball mill with sulfur edge-functionalized carbon", JOURNAL OF POWER SOURCES, vol. 430, pages 112 - 119 * |
| 高新余;: "提高球磨机磨球性能的技术研究及应用", 矿业快报, no. 06 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116646503B (en) | 2024-08-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101758967B1 (en) | Battery | |
| CN107482182B (en) | Carbon-coated ion-doped manganese phosphate lithium electrode material and preparation method thereof | |
| CN109755489B (en) | Preparation of sodium vanadium fluorophosphate/carbon compound and application of compound | |
| CN107910532A (en) | A kind of preparation method of graphene coated nickle cobalt lithium manganate composite material | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| Yang et al. | Nickel cobalt selenides on black phosphorene with fast electron transport for high-energy density sodium-ion half/full batteries | |
| CN114497473B (en) | N-doped porous carbon coated Mn-Co-Ni oxide core-shell structure electrode material and preparation method and application thereof | |
| CN112952047A (en) | Preparation method of carbon-loaded potassium vanadate and application of carbon-loaded potassium vanadate in potassium ion battery | |
| CN110620270B (en) | Secondary copper-zinc battery | |
| CN113611866B (en) | Flexible self-supporting sodium ion battery negative electrode material and preparation method thereof | |
| CN111048765B (en) | Preparation method of battery composite electrode material | |
| Zhao et al. | A CoSe 2-based 3D conductive network for high-performance potassium storage: enhancing charge transportation by encapsulation and restriction strategy | |
| CN105449294A (en) | Battery | |
| CN116646503B (en) | Preparation method of carbon-coated transition metal telluride and application of carbon-coated transition metal telluride in water-based zinc ion battery | |
| CN112186166A (en) | Molybdenum/cobalt oxide-carbon composite material and preparation method thereof, lithium ion battery negative electrode piece and lithium ion battery | |
| CN116759584A (en) | Ultrahigh specific surface area current collector with oxide/carbon composite deposited on surface and preparation method and application thereof | |
| CN115133145B (en) | Aqueous lithium/sodium ion battery based on nickel hydroxide positive electrode and titanium-based ion-intercalated negative electrode | |
| CN116544371A (en) | Positive electrode material, sodium ion battery and electric equipment | |
| CN113422059B (en) | High-voltage carbon fluoride composite cathode material and preparation method thereof | |
| CN115703651B (en) | Oxide type lithium ion battery anode material containing high-valence variable-valence metal and preparation method thereof | |
| CN112242525B (en) | Nitrogen-doped carbon-coated vanadium manganese sodium phosphate composite material and preparation method and application thereof | |
| CN115036502A (en) | Based on ZnCo 2 O 4 Method for preparing sodium ion battery cathode material by hollow carbon nanorings and application | |
| CN114843459A (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN107706389B (en) | Core-shell structure composite material containing transition metal phosphate and construction method and application thereof | |
| CN111628163B (en) | De-intercalation type vanadium-based negative electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |