CN115084501A - High-entropy compound for positive electrode of zinc ion battery and preparation method thereof - Google Patents
High-entropy compound for positive electrode of zinc ion battery and preparation method thereof Download PDFInfo
- Publication number
- CN115084501A CN115084501A CN202210601518.5A CN202210601518A CN115084501A CN 115084501 A CN115084501 A CN 115084501A CN 202210601518 A CN202210601518 A CN 202210601518A CN 115084501 A CN115084501 A CN 115084501A
- Authority
- CN
- China
- Prior art keywords
- entropy
- ion battery
- positive electrode
- zinc ion
- zinc
- 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.)
- Pending
Links
Images
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
- H01M4/62—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the field of zinc ion batteries, in particular to a high-entropy compound for a zinc ion battery anode and a preparation method thereof. The molecular formula of the high-entropy compound for the positive electrode of the zinc ion battery is M a X b In the molecular formula, M is a metal element selected from at least five of Fe, Co, Ni, Cu, Mn, Cr, Ti, V, Nb, Mo, Mg and Zn; x is O, S, Se, I or C; a: b is 1:1, 1:2, 2:3, 3:4 or 3: 2. The high-entropy compound (comprising high-entropy oxide, high-entropy sulfide, high-entropy selenide, high-entropy iodide and high-entropy carbide) is selected as the positive electrode material of the zinc ion battery, so that the cycling stability, the energy density and the specific capacity of the zinc ion battery can be effectively improved.
Description
Technical Field
The invention relates to the field of zinc ion batteries, in particular to a high-entropy compound for a zinc ion battery anode and a preparation method thereof.
Background
The development of novel batteries friendly to the environment has become a global trend, and people have raised higher and higher requirements on the aspects of miniaturization, light weight, high energy, high power, environmental friendliness and the like of the batteries. Among the most important performance criteria of a battery are storage capacity and cycling stability, i.e., maintaining a high number of charge and discharge cycles without losing storage capacity.
Currently, lithium ion batteries are widely used in the market of portable devices as an efficient energy storage device, but due to some defects of the lithium ion batteries, people are seeking another alternative battery. The zinc ion battery has the advantages of environmental friendliness, rich earth surface content, high energy density, high power density, relatively low oxidation-reduction potential and the like, and is expected to replace a lithium ion battery.
However, the anode material of the zinc ion battery has low selectivity, generally being Mn-based and V-based materials, and such materials still face great difficulties in practical application. For example, Mn-based materials cause elution of elements due to the J-T effect of Mn to cause a large capacity fade, and V-based materials cannot well match the safety characteristics of aqueous batteries because V has a large toxicity.
Therefore, development of a positive electrode material for a zinc ion battery having both high capacity and high safety is urgently required.
Disclosure of Invention
The invention aims to provide a high-entropy compound for a zinc ion battery positive electrode and a preparation method thereof, and overcomes the defects of the existing Mn-based material and V-based material by taking the high-entropy compound as a zinc ion battery positive electrode material.
Another object of the present invention is to provide a zinc ion battery using a high-entropy compound as a positive electrode material, which has excellent electrochemical properties, and more excellent cycle and rate performance.
In a first aspect, the invention provides a high-entropy compound for a zinc-ion battery positive electrode, wherein the molecular formula is M a X b ，
In the molecular formula, M is a metal element and is selected from at least five of Fe, Co, Ni, Cu, Mn, Cr, Ti, V, Nb, Mo, Mg and Zn;
x is O, S, Se, I or C;
a: b is 1:1, 1:2, 2:3, 3:4 or 3: 2.
The high-entropy material is a material which can customize the types and contents of elements and has componentsHuge adjusting space, unique entropy effect, adjustable material performance (cocktail effect) and the like. The high-entropy material comprises a plurality of metal elements (usually at least 5 elements), and each element system can show different structures, so that the high-entropy material has good adjustability. Therefore, high-entropy materials are used as the anode materials of lithium ion batteries and sodium ion batteries in the prior art, but the related materials are essentially rich in working ions (Li) + ,Na + ) The layered oxide is brought by multi-element doping, and the long-range order of the structure is kept to a certain extent. Furthermore, in the zinc ion battery system, Zn is contained 2+ Charge density ratio of (II) to (III) + 、Na + Much more, the existing high-entropy materials in the lithium sodium research system can cause the collapse of the material structure due to the excessive electrostatic repulsive force to cause poor electrochemical performance, which is the result of the essential difference of working ions, so the high-entropy materials in the existing lithium sodium research system can not bring more excellent electrochemical performance to the zinc ion battery. Therefore, high-entropy materials which are more advanced, excellent and have higher disorder degree than the existing lithium-sodium high-entropy positive electrode need to be developed for the zinc-ion battery to solve the core problem of large charge density. According to research, the invention discovers that the high-entropy compound (comprising high-entropy oxide, high-entropy sulfide, high-entropy selenide, high-entropy iodide and high-entropy carbide) is selected as the positive electrode material of the zinc ion battery, so that the cycling stability, the energy density and the specific capacity of the zinc ion battery can be effectively improved.
According to the high-entropy compound for the positive electrode of the zinc-ion battery, metal elements in the high-entropy compound are in an equimolar ratio.
According to the high-entropy compound for the positive electrode of the zinc-ion battery provided by the invention, when X is O, M is selected from five of Fe, Co, Ni, Cu, Mn, Cr, Mg and Zn, and a: b is 1:1 or 3: 4;
when X is S, M is selected from five of Fe, Co, Ni, Cu, Mn, Cr and Ti, and a: b is 1:1, 1:2, 2:3, 3:4 or 3: 2.
According to the high-entropy compound for the positive electrode of the zinc-ion battery, provided by the invention, the high-entropy compound is of a single-phase structure, including but not limited to a rock salt, perovskite or spinel structure.
The single-phase structure of the high-entropy compound brings the characteristics of a plurality of compounds prepared by traditional compounding and doping, and is beneficial to improving the cycle stability and energy density of the electrode material.
Further, the invention provides a high-entropy compound for a zinc ion battery anode, which is the high-entropy oxide M a O b Fluorine dopant or chlorine dopant.
The research of the invention finds that the doping of fluorine and chlorine anions is carried out on the basis of introducing the metal cation doping, so that the conductivity of the electrode material can be improved, and the dissolution of ions can be inhibited.
In a second aspect, the invention provides a preparation method of the high-entropy compound for the positive electrode of the zinc-ion battery.
The preparation method provided by the invention comprises the following steps: and (3) carrying out mixing reaction on all metal source substances in a hydrothermal, sol-gel or high-energy ball milling mode to obtain a high-entropy compound precursor, and then calcining the precursor.
In the above preparation method, the metal source substance may be an oxide, a metal salt, or the like of a metal. The metal source substances are used in equimolar ratio. The hydrothermal method, the sol-gel method and the high-energy ball milling method adopt conventional operation methods in the field, wherein the hydrothermal temperature is controlled at 170 ℃ for 15 hours, the calcining temperature is controlled at 400 ℃ and the calcining time is controlled at 2 hours.
According to the preparation method provided by the invention, when X is S, the preparation method comprises the following steps: carrying out high-energy ball milling on each metal or sulfide thereof and sulfur powder in an inert atmosphere.
According to embodiments of the present invention, when the metal has multiple valence states, the metal sulfide of the appropriate valence state is selected according to the molecular formula of the target high entropy sulfide.
According to an embodiment of the present invention, the inert atmosphere may be selected from a high purity argon atmosphere.
According to the embodiment of the invention, the high-energy planetary ball mill is adopted for high-energy ball milling, the rotating speed is controlled at 100-.
According to the preparation method provided by the invention, when the positive electrode material of the zinc ion battery is the high-entropy oxide M a O b The preparation method comprises the following steps: subjecting a high-entropy oxide M a O b High-energy ball milling is carried out with zinc fluoride in inert atmosphere.
According to the preparation method provided by the invention, when the positive electrode material of the zinc ion battery is the high-entropy oxide M a O b The preparation method comprises the following steps: subjecting a high-entropy oxide M a O b And carrying out high-energy ball milling with zinc chloride in inert atmosphere.
According to the embodiment of the invention, the high-energy ball milling is carried out by adopting a high-energy planetary ball mill.
In a third aspect, the invention provides a zinc ion battery, which comprises a positive electrode material, a negative electrode material and an electrolyte, wherein the positive electrode material comprises any one of the high-entropy compounds for the positive electrode of the zinc ion battery.
According to the zinc ion battery provided by the invention, the negative electrode material is a zinc sheet; the electrolyte is an aqueous electrolyte or a non-aqueous electrolyte.
According to an embodiment of the present invention, the aqueous electrolyte may be 1 to 5mol l -1 Zn(OTF) 2 、1-5molL -1 ZnSO 4 Or Zn (NO) 3 ) 2 An aqueous solution; the nonaqueous electrolyte may be 0.1 to 0.8mol L -1 Zn(OTF) 2 Acetonitrile solution.
The invention provides a high-entropy compound for a zinc ion battery anode and a preparation method thereof, various high-entropy materials are prepared by various methods and are applied to a zinc ion battery, and the systems are found to show excellent battery performance, so that the high-entropy compound has good scientific research value, and the water-based battery is more expected to be commercialized.
Drawings
FIG. 1 shows the results obtained in example 1 (FeCoNiCuMn) 3 O 4 Scanning electron microscope images of;
FIG. 2 shows the results obtained in example 1 (FeCoNiCuMn) 3 O 4 XRD pattern of (a);
FIG. 3,FIG. 4 shows the results obtained in example 1 (FeCoNiCuMn) 3 O 4 A charge-discharge curve and a cycle performance chart of a zinc ion aqueous battery equipped as a positive electrode material;
FIGS. 5 and 6 show examples 1 (FeCoNiCuMn) 3 O 4 A charge-discharge curve and a cycle performance chart of a zinc ion nonaqueous battery equipped as a positive electrode material;
FIG. 7 shows the results obtained in example 2 (FeCoNiCrMn) 3 O 4 XRD pattern of (a);
FIG. 8 shows the results obtained in example 2 (FeCoNiCrMn) 3 O 4 A charge/discharge curve of a zinc ion aqueous battery equipped as a positive electrode material;
FIG. 9 shows the results obtained in example 2 (FeCoNiCrMn) 3 O 4 A charge/discharge curve of a zinc ion nonaqueous battery mounted as a positive electrode material;
FIG. 10 is an XRD pattern of (FeMnNiCoCr) S in example 3;
FIG. 11 is a charge and discharge curve of a zinc ion aqueous system cell assembled with (FeMnNiCoCr) S as a positive electrode material in example 3;
FIG. 12 is the XRD pattern of (FeMnNiTiCr) S in example 4;
FIG. 13 is a charge/discharge curve of a zinc ion nonaqueous battery equipped with (FeMnNiTiCr) S as a positive electrode material in example 4;
FIG. 14 is a charge/discharge curve of a zinc ion aqueous battery equipped with Zn (HEO) F as a positive electrode material in example 9;
FIG. 15 is a scanning electron micrograph of Zn (HEO) Cl of example 10;
FIG. 16 is an XRD pattern of Zn (HEO) Cl in example 10;
FIG. 17 is a charge/discharge curve of a zinc ion aqueous battery equipped with Zn (HEO) Cl as a positive electrode material in example 10;
FIG. 18 is an XRD pattern of (MgCoNiCuZn) O in example 11;
fig. 19 is a charge/discharge curve of a zinc ion aqueous battery equipped with (MgCoNiCuZn) O as a positive electrode material in example 11.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise specified, reagents and equipment used in the following examples are commercially available.
Example 1
This example provides a high entropy oxide HEO of the formula FeCoNiCuMn 3 O 4 (Note that, here, the molecular formula is actually Fe) 0.6 Co 0.6 Ni 0.6 Cu 0.6 Mn 0.6 O 4 I.e., five metals of FeCoNiCuMn are in equal molar ratio, the sum in brackets is 1, the same is as below), the preparation method is as follows:
0.6g of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO20-PPO70-PEO20, Pluronic P123) was dissolved in 11.25ml of ethanol and 7.5ml of H were added 2 O and 36ml of ethylene glycol to form a homogeneous solution, and 0.3mmol of Co (Ac) was added to the mixed solution under vigorous stirring 2 ·4.H 2 O、0.3mmolNi(Ac) 2 ·4.H 2 O、0.3mmolMn(Ac) 2 ·4.H 2 O、0.3mmolCu(Ac) 2 ·.H 2 O、0.3mmolFe(Ac) 2 ·4.H 2 And O and 0.21g of hexamethylenetetramine are stirred vigorously for 45min, the solution is transferred to a 100ml stainless steel high-pressure hydrothermal kettle, the temperature is increased to 170 ℃ (15h), the solution is cooled to room temperature, the product is washed for a plurality of times (suction filtration) by water and ethanol, the product is dried at 60 ℃ to obtain a high-entropy oxide precursor, the obtained precursor is transferred to a crucible and is placed into a muffle furnace to be calcined for 2h at 400 ℃, and the final spinel phase HEO is obtained, wherein the scanning electron microscope image of the final spinel phase HEO is shown in figure 1, and the XRD image is shown in figure 2.
The obtained high-entropy oxide is used as a zinc ion battery anode material to assemble a zinc ion battery and test the zinc ion battery, and the method specifically comprises the following steps:
obtained (FeCoNiCuMn) 3 O 4 Ketjen black, PVDF according to 6: 3: 1, adding NMP to form slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, drying the carbon paper in a vacuum oven at 80 ℃ for 10h, using the obtained pole piece as a positive electrode, and using 1mol L of electrolyte -1 Zn(OTF) 2 Aqueous solution (Zinc triflate) (aqueous), or 0.3mol L -1 Zn(OTF) 2 Acetonitrile solution (nonaqueous system) and high-purity zinc sheet as negative electrodeThe electrochemical performance of the assembled battery was tested, and the charge/discharge curve and cycle performance in the water-based battery are shown in fig. 3 and 4, and the charge/discharge curve and cycle performance in the non-water-based battery are shown in fig. 5 and 6.
Example 2
This example provides a high entropy oxide HEO of the formula FeCoNiCrMn 3 O 4 The preparation method was the same as in example 1, in which the Cu element was replaced by Cr element. Obtained (FeCoNiCrMn) 3 O 4 The XRD pattern of (A) is shown in FIG. 7.
The obtained high-entropy oxide is used as a zinc ion battery anode material to assemble a zinc ion battery and test the zinc ion battery, and the method specifically comprises the following steps:
obtained (FeCoNiCrMn) 3 O 4 Ketjen black, PVDF according to 6: 3: 1, adding NMP to form slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, drying the carbon paper in a vacuum oven at 80 ℃ for 10h, applying the obtained pole piece to a positive electrode, and using 1mol L of electrolyte -1 Zn(OTF) 2 Aqueous solution (aqueous), or 0.3mol L -1 Zn(OTF) 2 The electrochemical performance of the zinc ion battery assembled by the acetonitrile solution (non-aqueous system) and the high-purity zinc sheet as the negative electrode is tested, and the charge-discharge curve in the aqueous battery is shown in fig. 8, and the charge-discharge curve in the non-aqueous battery is shown in fig. 9.
Example 3
This example provides a high-entropy sulfide HES, whose molecular formula is (FeMnNiCoCr) S, and the preparation method is as follows:
weighing corresponding metal sulfide (FeS, MnS, Ni) according to respective metal-sulfur ratio 3 S 2 、CoS 2 ) And carrying out ball milling on the Cr powder and the sulfur powder in a high-purity argon atmosphere by using a high-energy planetary ball mill. The XRD pattern of the resulting (FeMnNiCoCr) S is shown in FIG. 10.
The obtained high-entropy sulfide is used as a zinc ion battery anode material to assemble a zinc ion battery and test the zinc ion battery, and the method specifically comprises the following steps:
the obtained (femmnnicocr) S, ketjen black, PVDF were mixed in a ratio of 6: 3: 1, adding NMP to form a slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, and heating to 80 DEG CDrying in a vacuum oven for 10h, applying the obtained pole piece to a positive electrode, and using 1mol L of electrolyte -1 Zn(OTF) 2 The electrochemical performance of the zinc ion battery assembled by the aqueous solution (water system) and the high-purity zinc sheet as the negative electrode is tested, and the charge and discharge curve is shown in fig. 11.
Example 4
The embodiment provides high-entropy sulfide HES, the molecular formula of which is (FeMnNiTiCr) S, and the preparation method comprises the following steps:
weighing corresponding metal sulfide (FeS, MnS, Ni) according to respective metal-sulfur ratio 3 S 2 、TiS 2 ) And carrying out ball milling on the Cr powder and the sulfur powder in a high-purity argon atmosphere by using a high-energy planetary ball mill. The XRD pattern of the resulting (FeMnNiTiCr) S is shown in FIG. 12.
The obtained high-entropy sulfide is used as a zinc ion battery anode material to assemble a zinc ion battery and test the zinc ion battery, and the method specifically comprises the following steps:
the obtained (femmnniticr) S, ketjen black and PVDF were mixed in accordance with a 6: 3: 1, adding NMP to form slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, drying the carbon paper in a vacuum oven at 80 ℃ for 10h, applying the obtained pole piece to a positive electrode, and using 0.3mol L of electrolyte -1 Zn(OTF) 2 The electrochemical performance of the zinc ion battery assembled by the acetonitrile solution (non-aqueous system) and the high-purity zinc sheet as the negative electrode is tested, and the charge-discharge curve is shown in fig. 13.
Example 5
This example provides a high entropy sulfide HES of the formula (FeMnNiCoCr) S 2 The preparation method comprises the following steps:
weighing corresponding metal sulfide (FeS) according to respective metal sulfur ratio 2 、MnS、Ni 3 S 2 、CoS 2 ) And carrying out ball milling on the Cr powder and the sulfur powder in a high-purity argon atmosphere by using a high-energy planetary ball mill.
Example 6
This example provides a high entropy sulfide HES of the formula (FeMnNiCoCr) 2 S 3 The preparation method comprises the following steps:
weighing corresponding metal sulfide (FeS, MnS, Ni) according to respective metal-sulfur ratio 3 S 2 、CoS 2 ) And carrying out ball milling on the Cr powder and the sulfur powder in a high-purity argon atmosphere by using a high-energy planetary ball mill.
Example 7
This example provides a high entropy sulfide HES of the formula (FeMnNiCoCr) 3 S 4 The preparation method comprises the following steps:
weighing corresponding metal sulfide (FeS, MnS, Ni) according to respective metal-sulfur ratio 3 S 2 、CoS 2 ) And carrying out ball milling on the Cr powder and the sulfur powder in a high-purity argon atmosphere by using a high-energy planetary ball mill.
Example 8
This example provides a high entropy sulfide HES of the formula (FeMnNiCoCr) 3 S 2 The preparation method comprises the following steps:
weighing corresponding metal sulfides (FeS, MnS and Ni) according to the respective metal sulfur ratio 3 S 2 ) And Co, Cr powder and sulfur powder, and ball milling is carried out in a high-purity argon atmosphere by using a high-energy planetary ball mill.
Example 9
This example provides a high entropy compound zn (HEO) F, wherein HEO: (FeCoNiCuMn) 3 O 4 The preparation method comprises the following steps:
preparing a HEO precursor through reverse coprecipitation, and then calcining at high temperature to obtain HEO. And (3) ball-milling the zinc fluoride and the HEO by adopting a high-energy planetary ball mill.
The obtained high-entropy compound is used as a zinc ion battery anode material to assemble a zinc ion battery and test, and specifically comprises the following steps:
the obtained zn (heo) F, ketjen black, PVDF was mixed in accordance with 6: 3: 1, adding NMP to form slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, drying the carbon paper in a vacuum oven at 80 ℃ for 10h, applying the obtained pole piece to a positive electrode, and using 1mol L of electrolyte -1 Zn(OTF) 2 The electrochemical performance of the zinc ion battery assembled by the aqueous solution (water system) and the high-purity zinc sheet as the negative electrode is tested, and the charge and discharge curve is shown in fig. 14.
Example 10
This embodiment provides aA high entropy compound Zn (HEO) Cl, wherein HEO: (FeCoNiCuMn) 3 O 4 The preparation method comprises the following steps:
preparing a HEO precursor through reverse coprecipitation, and then calcining at high temperature to obtain HEO. And (3) carrying out ball milling on the zinc chloride and the HEO by adopting a high-energy planetary ball mill. A WC ball mill pot (volume 50ml) and WC balls (diameter 4mm) were used. The ball milling process is carried out under an Ar atmosphere. The prepared powder was collected and stored in a glove box filled with Ar atmosphere. The scanning electron micrograph of the obtained Zn (HEO) Cl is shown in FIG. 15, and the XRD map is shown in FIG. 16.
The obtained high-entropy compound is used as a zinc ion battery anode material to assemble a zinc ion battery and is tested, and the method specifically comprises the following steps:
the obtained zn (heo) Cl, ketjen black, PVDF were mixed according to 6: 3: 1, adding NMP to form slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, drying the carbon paper in a vacuum oven at 80 ℃ for 10h, applying the obtained pole piece to a positive electrode, and using 1mol L of electrolyte -1 Zn(OTF) 2 In the aqueous solution (water system), the negative electrode is a high-purity zinc sheet, and the high-purity zinc sheet is used as the negative electrode to assemble the zinc ion battery, the electrochemical performance of the zinc ion battery is tested, and the charge-discharge curve is shown in fig. 17.
Example 11
This example provides a high-entropy oxide HEO with a molecular formula of (MgCoNiCuZn) O, and the preparation method is as follows:
equimolar of MgCl 2 〃6H 2 O、ZnCl 2 、CoCl 2 、CuCl 2 And Ni (Ac) 2 〃4H 2 And performing ball milling on the O in a high-purity argon atmosphere by using a high-energy planetary ball mill. The mixed powder was then calcined in air at 900 ℃ for 4 hours (5 ℃/min) to obtain the desired oxidized crystalline phase. The XRD pattern is shown in FIG. 18.
The obtained high-entropy oxide is used as a zinc ion battery anode material to assemble a zinc ion battery and test the zinc ion battery, and the method specifically comprises the following steps:
the resulting (MgCoNiCuZn) O, ketjen black, PVDF was mixed in accordance with 6: 3: 1, adding NMP to form slurry, uniformly coating the slurry on carbon paper with the diameter of 8mm, drying the carbon paper in a vacuum oven at 80 ℃ for 10h, and applying the obtained pole piece to a positive electrode and electrolyteWith 1mol of L -1 Zn(OTF) 2 The electrochemical performance of the zinc ion battery assembled by the aqueous solution (water system) and the high-purity zinc sheet as the negative electrode is tested, and the charge-discharge curve is shown in fig. 19.
Example 12
This example provides a high entropy carbide with the formula TiVNbMoAlC 3 The preparation method comprises the following steps:
the molar ratio of Ti, V, Nb, Mo and Al metal element powder is 1:1:1:1:1, and the mixture is ground with zirconia balls in a polyethylene tank. The ball-milled powder was transferred to an alumina crucible and sintered for 4 hours in a conventional tube furnace equipped with 1600 c alumina tubes. The heating rate is 3.5 ℃ for min -1 . A constant Ar flow was maintained throughout the run until the sample reached room temperature. After cooling, the powder was ground to homogeneity.
Example 13
This example provides a high entropy carbide of the formula TiVCrMoAlC 3 The preparation method comprises the following steps:
the molar ratio of Ti, V, Cr, Mo and Al is 1:1:1:1, and the mixture is ground with zirconia balls in a polyethylene tank. The ball-milled powder was transferred to an alumina crucible and sintered for 4 hours in a conventional tube furnace equipped with a 1600 c alumina tube. The heating rate is 3.5 ℃ for min -1 . A constant Ar flow was maintained throughout the run until the sample reached room temperature. After cooling, the powder was ground to homogeneity.
Example 14
This example provides a high-entropy selenide HESe, whose molecular formula is (femmnnicor) Se, and the preparation method is substantially similar to that of example 3, which is not repeated herein.
Example 15
This example provides a high-entropy iodide HEI, whose molecular formula is (FeMnNiCoCr) I, and the preparation method is substantially similar to that of example 3, which is not repeated herein.
The performance of the high-entropy compounds obtained in examples 12 to 15 as positive electrode materials for zinc ion batteries was tested by the same method as in example 1, and the results showed that they also had good battery performance when applied to both aqueous and non-aqueous systems.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, it is intended that all such modifications and alterations be included within the scope of this invention as defined in the appended claims.
Claims (10)
1. A high-entropy compound used for a zinc ion battery anode is characterized in that the molecular formula is M a X b ，
In the molecular formula, M is a metal element and is selected from at least five of Fe, Co, Ni, Cu, Mn, Cr, Ti, V, Nb, Mo, Mg and Zn;
x is O, S, Se, I or C;
a: b ═ 1:1, 1:2, 2:3, 3:4 or 3: 2.
2. A high entropy compound for zinc ion battery positive electrode in accordance with claim 1, characterized in that the metal elements in the high entropy compound are in equimolar ratio.
3. High entropy compound for a zinc-ion battery positive electrode according to claim 1, characterized in that,
when X is O, M is selected from five of Fe, Co, Ni, Cu, Mn, Cr, Mg and Zn, and a: b is 1:1 or 3: 4;
when X is S, M is selected from five of Fe, Co, Ni, Cu, Mn, Cr and Ti, and a: b is 1:1, 1:2, 2:3, 3:4 or 3: 2.
4. A high entropy compound for use in a zinc ion battery positive electrode according to any of claims 1 to 3, characterized in that the high entropy compound is a single phase structure, including but not limited to a rock salt, perovskite or spinel structure.
5. High-entropy compound for positive electrode of zinc ion batteryCharacterized by being a high-entropy oxide M a O b Wherein M, a and b are as defined in claim 1.
6. A method for preparing a high entropy compound for a zinc ion battery positive electrode as claimed in any one of claims 1 to 4, characterized by comprising: and (3) carrying out mixing reaction on all metal source substances in a hydrothermal, sol-gel or high-energy ball milling mode to obtain a high-entropy compound precursor, and then calcining the precursor.
7. The method according to claim 6, wherein when X is S, the method comprises: and carrying out high-energy ball milling on each metal or sulfide thereof and sulfur powder in an inert atmosphere.
8. A process for the preparation of a high entropy compound for use in a zinc ion battery positive electrode as claimed in claim 5, which comprises subjecting a high entropy oxide M to a O b And carrying out high-energy ball milling with zinc fluoride or zinc chloride in inert atmosphere.
9. A zinc ion battery comprising a positive electrode material, a negative electrode material and an electrolyte, the positive electrode material comprising the high-entropy compound for a positive electrode of a zinc ion battery as claimed in any one of claims 1 to 5.
10. The zinc-ion battery of claim 9, wherein the negative electrode material is a zinc sheet; the electrolyte is an aqueous electrolyte or a non-aqueous electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210601518.5A CN115084501A (en) | 2022-05-30 | 2022-05-30 | High-entropy compound for positive electrode of zinc ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210601518.5A CN115084501A (en) | 2022-05-30 | 2022-05-30 | High-entropy compound for positive electrode of zinc ion battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115084501A true CN115084501A (en) | 2022-09-20 |
Family
ID=83248417
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210601518.5A Pending CN115084501A (en) | 2022-05-30 | 2022-05-30 | High-entropy compound for positive electrode of zinc ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115084501A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925392A (en) * | 2022-12-13 | 2023-04-07 | 郑州航空工业管理学院 | Transition metal high-entropy ceramic oxide composite material powder and preparation method thereof |
| CN116169280A (en) * | 2023-03-07 | 2023-05-26 | 北京工业大学 | High-entropy compound for positive electrode of aluminum ion battery and preparation method thereof |
| CN116715281A (en) * | 2023-06-01 | 2023-09-08 | 南京工业大学 | High-entropy fluoride composite asphalt-based carbon material and preparation method and application thereof |
| CN117105288A (en) * | 2023-10-25 | 2023-11-24 | 河南师范大学 | Preparation method and application of high-entropy vanadium-based oxide material |
-
2022
- 2022-05-30 CN CN202210601518.5A patent/CN115084501A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115925392A (en) * | 2022-12-13 | 2023-04-07 | 郑州航空工业管理学院 | Transition metal high-entropy ceramic oxide composite material powder and preparation method thereof |
| CN116169280A (en) * | 2023-03-07 | 2023-05-26 | 北京工业大学 | High-entropy compound for positive electrode of aluminum ion battery and preparation method thereof |
| CN116715281A (en) * | 2023-06-01 | 2023-09-08 | 南京工业大学 | High-entropy fluoride composite asphalt-based carbon material and preparation method and application thereof |
| CN116715281B (en) * | 2023-06-01 | 2024-04-12 | 南京工业大学 | High-entropy fluoride composite asphalt-based carbon material and preparation method and application thereof |
| CN117105288A (en) * | 2023-10-25 | 2023-11-24 | 河南师范大学 | Preparation method and application of high-entropy vanadium-based oxide material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115084501A (en) | High-entropy compound for positive electrode of zinc ion battery and preparation method thereof | |
| JP6564397B2 (en) | Doped nickelate material | |
| CN107968202A (en) | A kind of positive electrode of nickel cobalt manganese core shell structure containing aluminium and preparation method thereof | |
| CN103825015B (en) | The preparation method of high compacted density nickle cobalt lithium manganate NCM523 ternary material | |
| CN106654210B (en) | A kind of nickelic positive electrode of high temperature long circulating lithium ion battery and preparation method thereof | |
| CN105655573B (en) | A kind of general preparative methods of the adjustable one-dimensional micro-nano structure manganese base lithium ion battery electrode material of draw ratio | |
| US20170271670A1 (en) | Anode materials for sodium-ion batteries and methods of making same | |
| JP6408097B2 (en) | Positive electrode active material and non-aqueous electrolyte secondary battery | |
| JPH08217452A (en) | Needle manganese complex oxide, production and use thereof | |
| CN107500355B (en) | A kind of preparation method being layered lepidocrocite type nanometer strip vanadium dioxide | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| US20190288326A1 (en) | Sodium ion battery cathodes | |
| JP6117718B2 (en) | Lithium composite oxide | |
| EP1233001A2 (en) | Lithium-manganese complex oxide, production method thereof and use thereof | |
| JPH0992285A (en) | Nonaqueous electrolyte lithium secondary battery | |
| KR102447292B1 (en) | Positive electrode active material, manufacturing method thereof, and non-aqueous electrolyte secondary battery | |
| CN114843469B (en) | MgFe 2 O 4 Modified P2/O3 type nickel-based layered sodium ion battery positive electrode material and preparation method thereof | |
| CN105914354A (en) | Sodium-rich type titanium matrix layered solid solution electrode material for room-temperature sodium ion battery and preparation method | |
| CN113078316B (en) | Lithium molybdate-coated lithium-rich manganese-based positive electrode material and preparation method and application thereof | |
| WO2018056139A1 (en) | Cathode active material and method of manufacturing same, and nonaqueous electrolyte secondary battery | |
| CN105185981A (en) | Preparation method of LiNi<x>Mn<2-x>O<4> cathode material | |
| CN117133906A (en) | Coated oxygen-site doped modified sodium ion battery positive electrode material and preparation method thereof | |
| CN111082044A (en) | Yttrium-doped lithium-rich manganese-based lithium ion battery positive electrode material and preparation method thereof, and lithium ion battery | |
| CN113415826A (en) | Preparation method of novel niobium-based oxide as negative electrode material of lithium ion battery | |
| CN113443652A (en) | Preparation method and application of octahedral lithium manganate |
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 |