CN114824195A - Composite negative electrode material for zinc battery, preparation method and application thereof - Google Patents
Composite negative electrode material for zinc battery, preparation method and application thereof Download PDFInfo
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- CN114824195A CN114824195A CN202210288317.4A CN202210288317A CN114824195A CN 114824195 A CN114824195 A CN 114824195A CN 202210288317 A CN202210288317 A CN 202210288317A CN 114824195 A CN114824195 A CN 114824195A
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- 239000011701 zinc Substances 0.000 title claims abstract description 90
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 239000007773 negative electrode material Substances 0.000 title abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000010949 copper Substances 0.000 claims abstract description 41
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010406 cathode material Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000011230 binding agent Substances 0.000 claims abstract description 3
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 239000010405 anode material Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 2
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- PONZBUKBFVIXOD-UHFFFAOYSA-N 9,10-dicarbamoylperylene-3,4-dicarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=N)C2=C1C3=CC=C2C(=N)O PONZBUKBFVIXOD-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229910017267 Mo 6 S 8 Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a composite cathode material for a zinc battery, a preparation method and application thereof, wherein the composite cathode material comprises metal zinc Zn and copper telluride Cu x A mixture of Te; the preparation method comprises the following steps: mixing copper telluride powder with zinc powder, and carrying out ball milling under the protective atmosphere of inert gas to obtain zinc powder coated with copper telluride; or grinding and mixing the copper telluride powder, the organic solvent and the binder uniformly, then coating the mixture on a zinc sheet, and drying the zinc sheet in vacuum to obtain the copper telluride coated zinc sheet. The composite negative electrode material is used in an aqueous zinc ion battery or a nonaqueous zinc ion battery. The invention can solve the problems of low capacity and high potential of zinc dendrite and embedded cathode material, and has outstanding electrochemistryCan be used.
Description
Technical Field
The invention belongs to the technical field of zinc ion batteries, and particularly relates to a composite negative electrode material for a zinc battery, a preparation method and application thereof.
Background
The zinc ion battery is concerned about because the metal zinc cathode has the advantages of higher theoretical capacity, low material cost, high safety, environmental protection and the like. At present, zinc ion batteries, including aqueous zinc ion batteries and nonaqueous zinc ion batteries, mainly use metallic zinc (Zn) as a negative electrode material. However, the metallic zinc negative electrode is not only liable to form zinc dendrites to pierce a battery separator to cause short-circuiting of the battery during long-term dissolution-deposition, but also liable to lose adhesion of excessively deposited zinc to cause material loss, thereby reducing the cycle life of the battery. Meanwhile, in an aqueous zinc ion battery, since the dissolution-deposition potential of zinc is close to the hydrogen evolution potential in an aqueous solution, the electrolyte is decomposed, resulting in a decrease in cycle performance. In addition, because the coulombic efficiency of the dissolution-deposition of zinc in the aqueous electrolyte is low, the consumption of the zinc metal negative electrode in the water-based zinc ion battery is far excessive at present, so that the energy density of the whole full battery is reduced sharply.
Development of embedded negative electrode materials is another development direction of aqueous zinc ion batteries. At present, the embedded anode materials reported are very limited, including Na 0.14 TiS 2 ，Mo 6 S 8 ，MoO 3 And PTCDI, etc. However, these negative electrode materials not only have a high discharge potential (>0.3V vs Zn 2+ /Zn), and the electrochemical reaction is complex, involving multiple pairs of charge and discharge platforms. In addition, most of these negative electrode materials have a low reversible capacity (<150mAh g -1 ). When applied in a full cell, the high potential, low capacity characteristics result in a full cell with a lower discharge voltage and energy density. Therefore, these conditions limit the practical application of the above-described zinc ion battery embedded negative electrode.
The characteristics of the zinc cathode and the embedded cathode material are combined, the embedded cathode does not have the problem of dendrite, but the potential of the material is higher and the capacity is lower; metallic zinc has the advantages of low potential and high specific capacity, but has dendrite problems. Therefore, how to make the two types of cathode materials good and short is a technical problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a composite negative electrode material for a zinc battery aiming at the defects of the prior art, and the negative electrode material can solve the problems of low capacity and high potential of zinc dendrites and embedded negative electrode materials.
In order to solve the technical problems, the invention adopts the following technical scheme:
a composite negative electrode material for zinc battery is composed of Zn and Cu telluride x A mixture of Te.
Preferably, the value range of x is more than or equal to 1 and less than or equal to 2, wherein the molar ratio of copper telluride to zinc is y, and the value range of y is more than or equal to 0.1 and less than or equal to 8.
Preferably, x is 1.33-1.81, and y is 0.4-4.
The invention also provides a preparation method of the composite anode material for the zinc battery, which comprises the following steps:
mixing copper telluride powder with zinc powder, and carrying out ball milling under the protective atmosphere of inert gas to obtain zinc powder coated with copper telluride;
or grinding and mixing the copper telluride powder, the organic solvent and the binder uniformly, then coating the mixture on a zinc sheet, and drying the zinc sheet in vacuum to obtain the copper telluride coated zinc sheet.
It is still another object of the present invention to provide a use of the above composite anode material for a zinc battery for an aqueous zinc ion battery or a non-aqueous zinc ion battery.
Compared with the prior art, the invention has the beneficial effects that:
1) the cathode material of the invention has different electrochemical reaction mechanisms, and the cathode material reported at present has Na 0.14 TiS 2 ，Mo 6 S 8 ，MoO 3 And PTCDI and the like and metallic zinc, wherein Na 0.14 TiS 2 、Mo 6 S 8 、MoO 3 And PTCDI contains only the insertion-desorption mechanism and zinc only the dissolution-deposition mechanism, while those of the present inventionThe composite negative electrode material has an insertion mechanism and a dissolution-deposition mechanism at the same time, and the principle of the mechanism is as follows: a continuous 'intercalation-deposition' type composite zinc cathode consisting of a low intercalation potential (<0.3V vs Zn 2+ Zn) embedded negative electrode and zinc metal negative electrode, when the embedding reaction is finished, the deposition reaction of zinc is carried out; when the intercalation potential of zinc is close to the deposition potential of zinc, the reaction that occurs at this time is a continuous "intercalation-deposition" reaction. The composite cathode material can simultaneously solve the problems of low capacity and high potential of zinc dendrites and the embedded cathode material;
2) the composite negative electrode material has the following outstanding electrochemical properties: one is the lowest potential (0.2V vs Zn) reported at present except for Zn 2+ Zn); secondly, a single and flat charging and discharging platform is provided; thirdly, the reversible capacity is higher and can exceed 200mAh g -1 (ii) a Fourthly, the composite material has excellent cycle performance, the cycle time is as long as 3500 weeks, and the capacity retention rate is almost 100 percent; fifthly, under the condition of deep discharge, the generation of zinc dendrite can still be effectively inhibited;
3) the electrochemical behavior of the cathode composite material can be controlled simply by regulating and controlling Cu in the composite material x Te and Zn; for example, when Cu x When the molar ratio of Te to Zn is 1, 320mAh g of the composite negative electrode can be realized -1 Specific capacity and an average discharge potential of 0.1V; when Cu x When the molar ratio of Te to Zn is 8, the composite negative electrode can realize 210mAh g -1 Specific capacity and an average discharge potential of 0.2V;
4) the zinc ion battery cathode material is applied to a zinc ion battery as a composite cathode material, and can effectively avoid the formation of zinc dendrites; when the method is applied to the water system zinc ion battery, the zinc dendrite and the hydrogen evolution side reaction can be inhibited, the advantages of low potential and long cycle performance can be exerted, and the full battery is ensured to have higher discharge voltage, energy density and stable cycle performance.
Drawings
FIG. 1 shows Cu obtained in example 1 of the present invention 1.81 Cycling stability of the Te and zinc composite in a symmetric cell.
FIG. 2 shows Cu obtained in example 2 of the present invention 1.75 Te is used as a charge-discharge curve of the cathode material of the water-based zinc ion battery.
FIG. 3 shows Cu obtained in example 3 of the present invention 1.75 The circulation stability of the Te and zinc composite material in the symmetrical battery;
FIG. 4 shows Cu obtained in example 4 of the present invention 1.75 The Te and zinc composite negative electrode is used as a negative electrode material of the water-system zinc ion battery, and is a cycle performance diagram in the whole battery;
FIG. 5 shows Cu obtained in example 4 of the present invention 1.75 The Te and zinc composite negative electrode is used as a negative electrode material of an aqueous zinc ion battery, and is used as a coulombic efficiency diagram in a full battery;
FIG. 6 shows Cu obtained in example 9 of the present invention 1.33 And (3) a circulation stability diagram of the Te and zinc composite negative electrode in an organic electrolyte.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
Example 1
Weigh 0.8g of Cu 1.81 The Te powder and 0.2g PVDF were dispersed in NMP solvent, ground and mixed in an agate mortar for 15 minutes, and then coated on 5.2g zinc plates. And then drying the zinc sheet in a vacuum drying oven at 120 ℃ for 12 hours, cooling to room temperature, and cutting into round sheets with the diameter of 8mm to obtain the composite electrode. The obtained electrodes are combined into a symmetrical button cell, 2mol/L Zn (CF) 3 SO 3 ) 2 The electrochemical performance of the aqueous solution as an electrolyte was tested, and the cycling stability is shown in fig. 1. FIG. 2 shows that at 0.5mAcm -2 At a current density of 10, the composite negative electrodeThe electrode has stable cycle performance within 00h, while the blank zinc electrode has poor cycle stability, and short circuit occurs within 200 h.
Example 2
0.8g of Cu was weighed in a mass ratio of 8:1:1, respectively 1.75 Te, 0.1g of conductive carbon black and 0.1g of PTFE were uniformly mixed in isopropanol, and then rolled by a roll mill to form a film, which was cut into a disk having a diameter of 8mm and pressed on a titanium mesh to prepare an electrode. The resulting electrode was used as a working electrode, a zinc sheet was used as a counter electrode and a reference electrode, and 2mol/L Zn (CF) 3 SO 3 ) 2 The aqueous solution is used as electrolyte to assemble the button cell. The electrochemical performance of the material is tested, and the charge and discharge curves are shown in figure 2. FIG. 2 shows that the prepared electrode was charged at 25mA g -1 The current density of (2) is 0.01-1.1V (vs. Zn) 2+ /Zn), has an average discharge potential of 0.2V and 198mAh g -1 The reversible capacity of (a).
Example 3
Weigh 0.8g of Cu 1.75 The Te powder and 0.2g PVDF were dispersed in NMP solvent, ground and mixed in an agate mortar for 15 minutes, and then coated on 5.2g zinc plates. And then drying the zinc sheet in a vacuum drying oven at 120 ℃ for 12 hours, cooling to room temperature, and cutting into round sheets with the diameter of 8mm to obtain the composite electrode. The obtained electrode is combined into a symmetrical button cell, 2mol/L Zn (CF) 3 SO 3 ) 2 The electrochemical performance of the aqueous solution as an electrolyte was tested, and the charge and discharge curves are shown in FIG. 3. FIG. 3 shows that at 0.25mAcm -2 The composite negative electrode has stable cycle performance within 800 h.
Example 4
Weigh 0.8g of Cu 1.75 Te powder and 0.2g PVDF were dispersed in NMP solvent, ground and mixed in an agate mortar for 15 minutes, and then coated on 5.2g zinc plate. And then drying the zinc sheet in a vacuum drying oven at 120 ℃ for 12 hours, cooling to room temperature, and cutting into round sheets with the diameter of 8mm to obtain the composite electrode. The obtained electrode was used as a negative electrode material, carbon-coated iodine was used as a positive electrode material, 2mol/L Zn (CF) 3 SO 3 ) 2 As electrolyte, to form a button cell full cell, and testing its electrochemistryThe performance, cycling stability, is shown in figures 4 and 5. FIGS. 4 and 5 show that the pressure drop at 1A g -1 The full-cell with the composite cathode has more stable cycle performance and coulombic efficiency under the current density of the anode.
Example 5
Weigh 0.4g of Cu 1.5 And ball-milling the Te powder and 0.6g of Zn powder in a high-energy ball mill at the speed of 300r/min for 4 hours to obtain a uniform composite material, then adding 0.05g of carbon black and 0.05g of PTFE into isopropanol, uniformly mixing, then rolling by a double-roll mill to form a film, cutting into a wafer with the diameter of 8mm, and pressing on a titanium mesh to prepare an electrode, thus obtaining the electrode in the embodiment 5.
Example 6
Weigh 0.4g of Cu 1.75 And ball-milling the Te powder and 0.1g of Zn powder in a high-energy ball mill at the speed of 300r/min for 4 hours to obtain a uniform composite material, then adding 0.05g of carbon black and 0.05g of PTFE into isopropanol, uniformly mixing, then rolling by a double-roll mill to form a film, cutting into a wafer with the diameter of 8mm, and pressing on a titanium mesh to prepare the electrode in the embodiment 6.
Example 7
Weigh 0.4g of Cu 1.33 And ball-milling the Te powder and 1g of Zn powder in a high-energy ball mill at the speed of 300r/min for 4 hours to obtain a uniform composite material, then adding 0.05g of carbon black and 0.05g of PTFE into isopropanol, uniformly mixing, then rolling by a double-roll mill to form a film, cutting into a wafer with the diameter of 8mm, and pressing on a titanium mesh to prepare the electrode in the embodiment 7.
Example 8
Weigh 0.2g of Cu 1.5 The Te powder and 0.1g PVDF were dispersed in NMP solvent, ground and mixed in an agate mortar for 15 minutes, and then coated on 2g zinc plates. Then, the zinc sheet was dried in a vacuum oven at 120 ℃ for 12 hours, cooled to room temperature, and cut into a wafer having a diameter of 8mm, to obtain the electrode of embodiment 8.
Example 9
Weigh 0.2g of Cu 1.33 The Te powder and 1g of Zn powder are ball milled for 4 hours in a high-energy ball mill at the speed of 300r/min to obtain uniform powderThen 0.05g of carbon black and 0.05g of PTFE are added into the composite material and evenly mixed in isopropanol, then a film is formed by rolling with a roll pair machine, and is cut into a circular sheet with the diameter of 8mm, and the circular sheet is pressed on a titanium net to form an electrode, thus obtaining the electrode in the embodiment 8. The obtained electrode is combined into a symmetrical button cell, 0.5mol/L Zn (CF) 3 SO 3 ) 2 The electrochemical performance of the organic electrolyte dissolved in acetonitrile and ethylene glycol is tested, and the charge-discharge curve is shown in figure 6. FIG. 6 shows that at 2A cm -2 The composite negative electrode has stable cycle performance under the current density of (2).
Cu suitable for use in the present invention x The Te and Zn composite anode material is not limited to the specific pure substances in the above embodiments, and may be other anode materials having similar functions and effects. For example, mixing TiS 2 Mixing the zinc oxide with Zn according to a certain mass ratio to be used as a zinc ion battery cathode material; or compounds containing more than one chalcogen element at the same time, e.g. by reacting Cu with a metal x Te 0.95 Se 0.05 The material is used as a negative electrode material of a zinc ion battery. In addition, Cu doped with other metal ions x Te is also the field of protection of the invention, e.g. Zn 0.15 Cu 1.85 Te is used as a negative electrode material of the zinc ion battery.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention.
Claims (5)
1. The composite cathode material for the zinc battery is characterized by comprising metal zinc Zn and copper telluride Cu x A mixture of Te.
2. The composite anode material for a zinc battery as claimed in claim 1, wherein x is in a range of 1. ltoreq. x.ltoreq.2, wherein the molar ratio of copper telluride to zinc is y in a range of 0.1. ltoreq. y.ltoreq.8.
3. The composite anode material for a zinc battery as claimed in claim 2, wherein x is in the range of 1.33. ltoreq. x.ltoreq.1.81, and y is in the range of 0.4. ltoreq. y.ltoreq.4.
4. A method for preparing a composite anode material for a zinc battery according to any one of claims 1 to 3, comprising the steps of:
mixing copper telluride powder with zinc powder, and carrying out ball milling under the protective atmosphere of inert gas to obtain zinc powder coated with copper telluride;
or grinding and mixing the copper telluride powder, the organic solvent and the binder uniformly, then coating the mixture on a zinc sheet, and drying the zinc sheet in vacuum to obtain the copper telluride coated zinc sheet.
5. Use of the composite anode material for a zinc battery according to any one of claims 1 to 3 in an aqueous zinc ion battery or a non-aqueous zinc ion battery.
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| 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 |
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| CN108321387A (en) * | 2017-12-26 | 2018-07-24 | 深圳先进技术研究院 | Telluro material is used as application of the negative electrode active material in sodium base Dual-ion cell, sodium tellurium Dual-ion cell and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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