CN114883522A - High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof - Google Patents
High-entropy-like multi-element layered transition metal oxide cathode material and preparation method and application thereof Download PDFInfo
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- CN114883522A CN114883522A CN202210415598.5A CN202210415598A CN114883522A CN 114883522 A CN114883522 A CN 114883522A CN 202210415598 A CN202210415598 A CN 202210415598A CN 114883522 A CN114883522 A CN 114883522A
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- transition metal
- entropy
- metal compound
- metal oxide
- ball milling
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- 229910000314 transition metal oxide Inorganic materials 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000010406 cathode material Substances 0.000 title claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 25
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011734 sodium Substances 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 18
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- 239000011591 potassium Substances 0.000 claims abstract description 18
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- 238000000137 annealing Methods 0.000 claims abstract description 13
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- 150000003623 transition metal compounds Chemical class 0.000 claims description 18
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
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- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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Images
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- 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
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/366—Composites as layered products
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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
- H01M4/48—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
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A high-entropy-like multi-element layered transition metal oxide cathode material, a preparation method and application thereof. General formula of the materialA x (M) y N z O 2 It is shown that the process of the present invention,Ais one or more than two of alkali metal elements uniformly combined,Mis a uniform combination of three or more of low electronegativity transition metal elements,None or more than two of high electronegativity elements are equally combined, and x is between0.4-1.0, y between 0.01-0.5, and z between 0.2-0.9, and can be prepared by ball milling, freeze-drying, solvothermal, sol-gel or coprecipitation, followed by annealing at high temperature to obtain the final product. The material contains five or more transition metal elements, has a large amount of lattice distortion and higher entropy, can inhibit structural collapse in the charging and discharging process, fully exerts the advantages of various elements, can be used as the anode material of lithium, sodium and potassium ion batteries, namely can realize excellent potassium, sodium and lithium storage performance under the synergistic effect, and has excellent capacity, multiplying power and cycling stability.
Description
Technical Field
The invention belongs to the technical field of electrochemical cells, and particularly relates to a high-entropy-like multi-element layered transition metal oxide positive electrode material, and a preparation method and application thereof.
Background
With the development of clean energy, the large-scale energy storage power station market puts new requirements on the current energy storage technology. Although lithium ion batteries in the current market occupy the mainstream, the problems of hidden troubles in supply and demand caused by limited lithium resources and high cost of the lithium ion batteries are increasingly prominent, so that the market needs a novel electrochemical energy storage technology with both cost and performance to adapt to the requirements of large-scale energy storage power stations.
The potassium ion battery has the advantages of electrochemical principle similar to that of the lithium ion battery, similar oxidation-reduction potential, low cost due to rich earth crust storage, use of cheaper aluminum foil as a current collector and the like, and is widely considered as an energy storage scheme with bright prospect.
In the current development of potassium ion batteries, the capacity and the rate of a negative electrode material are basically guaranteed, but a breakthrough cannot be made in the research aspect of a positive electrode material because the large ionic radius of potassium ions makes the potassium ions difficult to be embedded and extracted in the positive electrode material, so that the lower capacity is caused. In addition, the larger ion radius also causes potassium ions to damage the original structure in the process of embedding and extracting the main body material, so that the problem of low capacity rapid attenuation is caused. In addition, the layered transition metal oxide can generate multiple phase change processes in the charge and discharge processes, which has negative effects on the structure and capacity of the material.
The most critical factor for developing the potassium ion battery anode is the selection of raw materials and a subsequent preparation mode, and the common optimization strategies of the active substances of the current potassium ion battery anode materials comprise the following categories, namely coating of carbon materials, pre-insertion of structural water, doping of multi-element metals, modification of fluoride coatings and the like.
Under the optimization strategy of the multi-element metal doping, the current research means is only limited in the aspects of single element doping, binary doping, ternary doping and the like, and the performance of the battery cannot be more optimized, so that aiming at the current situation, the patent provides that the concept of high entropy is introduced into the positive electrode material of the potassium ion battery to modify the layered metal oxide material, a more characteristic high entropy multi-element positive electrode energy storage material is designed, and more inactive ion doping assistance is used while the valence change effect of active ions is exerted to realize better performance.
The prior patents of the high-entropy cathode material are only limited to Li high-specific-energy batteries, and the field focused by the application is the cathode material of potassium-ion batteries.
Disclosure of Invention
Aiming at the defects of low capacity, poor rate performance and the like, the invention provides a similar high-entropy multi-element layered transition metal oxide positive electrode material, a preparation method and application thereof.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
the high-entropy-like multi-element layered transition metal oxide anode material has the general formulaA x (M) y N z O 2 The general formula is shown in the specification, wherein,Ais one or a combination of two equimolar amounts of element K, Na or Li;Mis the elements Ni,A combination of at least three equimolar amounts of Co, Fe, Ti, V, Cr, Zn, Cu, Mg or Al;Nis the combination of one or two of Mn, Mo, W, Bi, Sb, Sn or Te in equal molar quantity, and x is between 0.4 and 1.0, y is between 0.01 and 0.5, and z is between 0.2 and 0.9.
The preparation method of the high-entropy-like multi-element layered transition metal oxide anode energy storage material comprises the following steps of: the first step is as follows: according to the general formula of the material design, preparing a uniform composite precursor by performing any one of physical ball milling, freeze drying, solvothermal, sol-gel or coprecipitation on a transition metal compound and an alkali metal compound; and secondly, annealing the precursor to obtain a final product.
The improvement wherein in the first step the transition metal compound is a transition metal oxide, transition metal hydroxide, transition metal carbonate, transition metal nitrate, transition metal oxalate, transition metal sulfate, transition metal chloride, transition metal sulfide, transition metal phosphide, or transition metal nitride.
The alkali metal compound in the first step may be a carbonate of lithium, sodium or potassium, a hydroxide of lithium, sodium or potassium, an oxalate of lithium, sodium or potassium, a nitrate of lithium, sodium or potassium, or a sulfate of lithium, sodium or potassium.
The improvement is that the physical ball milling method in the first step is to put the transition metal compound and the alkali metal compound into a ball milling tank for ball milling for 5-15h, and then wash and dry the product, wherein the ball milling speed is 400-1000 rpm; adding a transition metal compound and an alkali metal compound into a centrifuge tube, adding ultrapure water, transferring into liquid nitrogen for freezing for 0.5h, and drying for 48h by using a freeze dryer; the solvothermal method comprises the steps of uniformly dissolving a transition metal compound in ethylene glycol or an aqueous solution of ethylene glycol, sealing the solution in a solvothermal reaction kettle, carrying out solvothermal reaction at the temperature of 100-220 ℃, wherein the reaction time is 10-20 h, carrying out suction filtration, cleaning, drying and grinding after the reaction is finished, and mixing a solvothermal reaction product with an alkali metal compound to obtain a uniform mixture.
The improvement is that the sol-gel method comprises the steps of adding a transition metal compound, citric acid and an alkali metal compound into ethylene glycol, stirring for 3 hours, carrying out a solvothermal reaction for 6 hours at the temperature of 130-150 ℃, and drying a product, wherein the molar weight of the citric acid and the alkali metal compound is 2 times that of the transition metal compound; the coprecipitation method comprises the steps of dissolving a transition metal compound in ultrapure water, dropwise adding the solution into 2-15mol/L alkali metal hydroxide solution, stirring at the rotation speed of 1000-1500 rpm for 5-24 h, sequentially and respectively carrying out suction filtration and cleaning with water and ethanol for three times, drying to obtain a corresponding transition metal hydroxide precursor, and then uniformly mixing the dried precipitate product with the alkali metal compound.
The improvement is that the annealing treatment in the second step specifically comprises the following steps: and placing the precursor in a muffle furnace or an oxygen plasma enhanced sintering furnace, annealing at the temperature of 450-1000 ℃ for 0.5-48h, and cooling to room temperature along with the furnace.
The high-entropy multi-element layered transition metal oxide anode energy storage material can be applied to anode materials of lithium, sodium and potassium ion batteries.
The design principle is as follows: taking five or more than five metal compounds as reaction raw materials and a multi-metal source, uniformly mixing the reaction raw materials and the multi-metal source by a physical ball milling method, a freeze drying method, a solvothermal method, a sol-gel method or a coprecipitation method, and then annealing the mixture in the air to obtain the corresponding high-entropy oxide anode. Because the positive electrode material is composed of more than five transition metal elements, a large amount of lattice distortion and a high entropy value exist in the material, the structural collapse caused by volume change in the charge and discharge process can be inhibited, the advantages of various elements can be fully exerted in the charge and discharge process, and the defects of other elements are inhibited, so that the high-entropy transition metal oxide positive electrode material prepared by the technology realizes excellent potassium storage, sodium storage and lithium storage performances under the synergistic effect, and has the performance characteristics of capacity, multiplying power and cycling stability of 'three highs'.
Has the advantages that:
compared with the prior art, the high-entropy-like multi-element layered transition metal oxide cathode material and the preparation method and application thereof have the following advantages:
1. the high-entropy-like multi-element layered transition metal oxide anode energy storage material is prepared by compounding at least five transition metal elements, a large amount of lattice distortion and a high entropy value exist in the material, the structural collapse caused by volume change in the charging and discharging process can be inhibited, the advantages of various elements can be fully exerted in the charging and discharging process, the weakness of other elements is inhibited, namely excellent potassium storage, sodium storage and lithium storage performances are realized under the synergistic effect, the high-entropy-like multi-element layered transition metal oxide anode energy storage material has the performance characteristics of capacity, multiplying power and cycling stability of 'three highs', the development of the potassium ion battery anode material has a new opportunity by introducing a high entropy concept, the development of the potassium ion battery anode material in the energy storage field is promoted, the potassium ion battery anode material is greatly promoted, great theoretical contribution and practical experience value are provided for the development of the electrochemical battery field in China, and the diversity and functionality of the potassium ion battery production are further widened, greatly increases the utilization of the existing resources and the recycled resources, and has higher material selection flexibility and functional promotion brought by multi-material collocation compared with the prior single layered metal oxide and simple one-two-three doping mode;
2. the high-entropy-like multi-element layered transition metal oxide anode energy storage material has a stable material structure prepared under a high-temperature reaction, does not generate a heterogeneous phase, has no specific micro morphology, belongs to the crystal category, has a peak type of XRD, has the general characteristics of the active substances of the anode materials of general potassium ion batteries, namely a K peak exists at about 10 degrees, is convenient to identify, and plays a great promoting role in improving the electrochemical properties of the battery materials;
3. the actual electrochemical performance of the high-entropy-like multi-element layered transition metal oxide anode energy storage material shows that 500 mA g in potassium ion half-cell -1 And under the test of a voltage window of 1.5-4.0V, 200 circles of charge and discharge can be carried out, and the capacity can be finally kept at 60 mAh g -1 Compared with the traditional potassium ion battery material, the electrochemical performance test specific capacity is improved and the cycle is stableThe qualitative is greatly enhanced.
Drawings
FIG. 1 is an XRD diagram of a transition metal oxide anode energy storage material prepared after ball milling annealing in example 1 of the present invention;
FIG. 2 is an SEM image of a transition metal oxide anode energy storage material prepared by ball milling in example 1 of the present invention;
FIG. 3 is a charge-discharge curve of electrochemical test of transition metal oxide positive energy storage material prepared by ball milling in example 1 of the present invention;
fig. 4 shows the electrochemical test long cycle performance of the transition metal oxide positive energy storage material prepared by ball milling in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and specific examples, which are only used for illustrating the present invention and are not limited to the following examples. It is intended that all modifications and equivalents of the technical aspects of the present invention be included within the scope of the present invention without departing from the spirit and scope of the technical aspects of the present invention.
The high-entropy-like multi-element layered transition metal oxide anode energy storage material has the general formulaA x (M) y N z O 2 The general formula is shown in the specification, wherein,Ais one or a combination of two equimolar amounts of element K, Na or Li;Mis the combination of at least three equimolar amounts of elements of Ni, Co, Fe, Ti, V, Cr, Zn, Cu, Mg or Al;Nis the combination of one or two of Mn, Mo, W, Bi, Sb, Sn or Te in equal molar quantity, and x is between 0.4 and 1.0, y is between 0.01 and 0.5, and z is between 0.2 and 0.9.
The preparation method of the high-entropy-like multi-element layered transition metal oxide anode energy storage material comprises the following steps of: the first step is as follows: according to a general formula of a material design, preparing a uniform composite precursor by any one of a physical ball milling method, a freeze drying method, a solvothermal method, a sol-gel method or a coprecipitation method for a transition metal compound and an alkali metal compound; and secondly, annealing the precursor to obtain a final product.
Example 1
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
in the first step, 0.35mol of manganese sesquioxide, 0.05mol of titanium dioxide, 0.05mol of nickel oxide, 0.025mol of ferric oxide and 0.05mol of magnesium oxide are weighed as one of raw materials, and 0.3mol of potassium carbonate is weighed as the second of raw materials to be used as an alkali metal source. Grinding and uniformly mixing all raw materials in a mortar;
step two, preparing two ball milling tanks, uniformly distributing the mixed material into the two ball milling tanks, adding ethanol to soak the surface of the material, adjusting the weight of the two ball milling tanks to be the same, putting the two ball milling tanks into a ball mill, performing the rotation speed of 500r/min, performing reverse ball milling for 0.5h after suspending for 0.5h after each ball milling, taking out the mixed material from the ball milling tanks after circulating for 10 times, and drying and grinding the mixed material to obtain a precursor material;
thirdly, reacting the precursor material in PECVD, keeping the reaction at 750 ℃ for 10h, and performing heat treatment to obtain the target material K 0.6 (NiFeTiMg) 0.05 Mn 0.7 O 2 。
The synthesized material was subjected to XRD test, and the test results are shown in fig. 1.
SEM tests were performed on the synthesized material, and the test results are shown in fig. 2.
As can be seen from FIGS. 1 and 2, the target material K of the present invention 0.6 (NiFeTiMg) 0.05 Mn 0.7 O 2 . In XRD of FIG. 1, a strong K peak exists at about 10 degrees, which indicates that K element exists in the target material and can be used as a positive electrode material of a potassium ion battery. In the SEM of fig. 2, the material is packed from particles into an assembly with mesopores and macropores, and the pore structure of the assembly is favorable for the infiltration of the electrolyte.
For target material K 0.6 (NiFeTiMg) 0.05 Mn 0.7 O 2 And assembling the potassium ion battery for the raw materials, and testing the performance of the battery.
Assembling the lithium ion battery:
the transition metal oxide anode energy storage material, acetylene black and PVDF (polyvinylidene fluoride) are mixed according to the mass ratio of 8: 1:1, adding NMP (N-methyl pyrrolidone) and stirring for 6 hours, uniformly coating the mixture on a copper foil by a scraper through a tape casting method, carrying out button cell loading operation in an argon atmosphere glove box, wherein a counter electrode is a lithium sheet, a diaphragm is a PP material, the concentration of electrolyte is 1 mol/L and is 1mol LiPF 6 Dissolved in 1L of a mixed solution of EC: DMC: EMC (volume ratio: 1: 1).
Assembling the sodium-ion battery:
the transition metal oxide anode energy storage material, acetylene black and PVDF (polyvinylidene fluoride) are mixed according to the mass ratio of 8: 1:1, adding NMP (N-methyl pyrrolidone) and stirring for 6 hours, uniformly coating the mixture on a copper foil by a doctor blade through a tape casting method, carrying out button cell loading operation in an argon atmosphere glove box, wherein a counter electrode is a sodium sheet, a diaphragm is made of glass fiber, the concentration of electrolyte is 2 mol/L and is 1mol NaPF 6 Dissolved in 1L of DIGLYME.
Assembling the potassium ion battery:
mixing the target material K 0.6 (NiFeTiMg) 0.05 Mn 0.7 O 2 Acetylene black and PVDF (polyvinylidene fluoride) according to the mass ratio of 8: 1:1, adding NMP (N-methyl pyrrolidone), mixing and stirring for 6 hours, uniformly coating the mixture on an aluminum foil by a doctor blade through a tape casting method, and carrying out operation of installing a button cell in an argon atmosphere glove box, wherein a counter electrode is a potassium sheet, a diaphragm is made of glass fiber, and electrolyte is 0.8 mol.L -1 KPF 6 The EC + DEC (volume ratio of 1:1) mixed solution of (1). The steps not mentioned in the assembly process are conventional steps for preparing the button cell, and are not described again here.
The assembled potassium ion battery was tested for charge and discharge and the test results are shown in FIG. 3 at 500A g -1 Under the current intensity and the voltage window test condition of 1.5-4.0V, the charging specific capacity of the first ring is 32.2 mAh g -1 The specific discharge capacity of the first ring is 80.7 mAh g -1 It can be seen that the charging and discharging curves are still gentle although they are slightly fluctuated.
The actual electrochemical performance of the quasi-high-entropy multi-element layered transition metal oxide anode energy storage material prepared by the invention is shown to be 500 mA g -1 Under the current intensity of (1.5) and the voltage window test condition of (4.0) V, the charging capacity of the first loop is 32.2 mAh g -1 The specific discharge capacity of the first ring is 80.7 mAh g -1 It can be seen that the charging and discharging curves are still gentle although they are slightly fluctuated.
The assembled potassium ion battery is tested for electrochemical performance and long cycle performance, and the test result is shown in figure 4, and the electrochemical performance is 500 mA g -1 The initial discharge specific capacity is 80.7 mAh g under the test conditions of the current intensity and the voltage window of 1.5-4.0V -1 After 200 cycles of long cycling, the cell possessed 42.2 mAh g -1 The specific capacity is retained, the average attenuation per ring is 0.238%, and the performance is in a higher level compared with the existing energy storage material of the potassium ion battery at present, so that the material has an excellent industrialization prospect.
Example 2
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
weighing 0.35mol of manganese acetate, 0.05mol of titanium dioxide, 0.05mol of nickel acetate, 0.025mol of iron acetate and 0.05mol of magnesium acetate as one of raw materials, and 0.2mol of lithium hydroxide and 0.2mol of potassium carbonate as the other raw material to serve as an alkali metal source;
step two, preparing two ball milling tanks, uniformly distributing the materials into the two ball milling tanks, adding ethanol to soak the surfaces of the materials, debugging the weight of the two ball milling tanks to be uniform, putting the two ball milling tanks into a ball mill to perform 600r/min of rotation speed, performing reverse ball milling for 0.5h after suspending for 0.5h after each ball milling, taking out the mixed materials from the ball milling tanks to perform drying and grinding to obtain precursor materials after circulating for 10 times;
thirdly, reacting the precursor material in PECVD, keeping the reaction at 950 ℃ for 10h, and performing heat treatment to obtain the target material K 0.4 Li 0.2 (NiFeTiMg) 0.05 Mn 0.7 O 2 。
Example 3
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
weighing 0.35mol of manganese oxalate, 0.05mol of titanium dioxide, 0.05mol of nickel oxalate, 0.025mol of iron oxalate and 0.05mol of magnesium oxalate as one of raw materials, and taking 0.2mol of potassium carbonate, 0.1mol of lithium hydroxide and 0.05mol of sodium carbonate as the other raw material as an alkali metal source;
step two, preparing two ball milling tanks, uniformly distributing the materials into the two ball milling tanks, adding ethanol to soak the surfaces of the materials, adjusting the weight of the two ball milling tanks to be uniform, putting the two ball milling tanks into a ball mill to perform 700r/min of rotation speed, performing reverse ball milling for 0.5h after suspending for 0.5h after each ball milling, and taking out the mixed materials from the ball milling tanks to perform drying and grinding to obtain precursor materials after circulating for 10 times;
thirdly, reacting the precursor material in PECVD, keeping the reaction at 750 ℃ for 10h, and performing heat treatment to obtain the target material K 0.4 Li 0.1 Na 0.1 (NiFeTiMg) 0.05 Mn 0.7 O 2 。
Example 4
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
weighing 0.35mol of manganese nitrate, 0.05mol of titanium dioxide, 0.05mol of nickel nitrate, 0.05mol of copper nitrate and 0.05mol of aluminum nitrate as one of raw materials, and taking 0.3mol of potassium carbonate as the other raw material as a potassium source;
step two, preparing two ball milling tanks, uniformly distributing the materials into the two ball milling tanks, adding ethanol to soak the surfaces of the materials, debugging the weight of the two ball milling tanks to be uniform, putting the two ball milling tanks into a ball mill to perform a rotation speed of 500r/min, performing reverse ball milling for 0.5h after suspending for 0.5h after each ball milling, taking out the mixed materials from the ball milling tanks to perform drying and grinding to obtain precursor materials after circulating for 10 times;
thirdly, reacting the precursor material in a muffle furnace, keeping the temperature at 750 ℃ for 10h, and performing heat treatment to obtain a target material K 0.6 (NiCuTiAl) 0.05 Mn 0.7 O 2 。
Example 5
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
the first step is as follows: weighing 0.5mol of tellurium dioxide, 0.05mol of titanium dioxide, 0.05mol of nickel chloride, 0.025mol of ferric oxide, 0.05mol of magnesium oxide and 0.05mol of copper oxide as one of raw materials, and 0.4mol of potassium carbonate as the other raw material as a potassium source;
step two, preparing two ball milling tanks, uniformly distributing the materials into the two ball milling tanks, adding ethanol to soak the surfaces of the materials, debugging the weight of the two ball milling tanks to be uniform, putting the two ball milling tanks into a ball mill to perform a rotation speed of 500r/min, performing reverse ball milling for 0.5h after suspending for 0.5h after each ball milling, taking out the mixed materials from the ball milling tanks to perform drying and grinding to obtain precursor materials after circulating for 10 times;
the third step: reacting the precursor material in PECVD (plasma enhanced chemical vapor deposition), keeping the reaction temperature at 650 ℃ for 8h, and performing heat treatment to obtain a target material K 0.8 (NiFeTiMgCu) 0.05 Te 0.4 O 2 。
Example 6
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
weighing 0.3mol of tellurium dioxide, 0.15mol of manganese oxide, 0.05mol of titanium dioxide, 0.05mol of nickel chloride, 0.025mol of ferric oxide and 0.05mol of magnesium oxide as one of raw materials, and taking 0.3mol of potassium carbonate as the other raw material as a potassium source;
step two, preparing two ball milling tanks, uniformly distributing the materials into the two ball milling tanks, adding ethanol to soak the surfaces of the materials, debugging the weight of the two ball milling tanks to be uniform, putting the two ball milling tanks into a ball mill to perform a rotation speed of 500r/min, performing reverse ball milling for 0.5h after suspending for 0.5h after each ball milling, taking out the mixed materials from the ball milling tanks to perform drying and grinding to obtain precursor materials after circulating for 10 times;
the third step: reacting the precursor material in PECVD (plasma enhanced chemical vapor deposition), keeping the reaction temperature at 650 ℃ for 10h, and performing heat treatment to obtain a target material K 0.6 (NiFeTiMg) 0.05 (TeMn) 0.3 O 2 。
EXAMPLE 7 Solvothermal Process
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
firstly, measuring 60ml of ethylene glycol, placing the ethylene glycol in a beaker, weighing 0.7mol of manganese acetate, 0.05mol of nickel acetate, 0.05mol of iron acetate and 0.05mol of magnesium acetate, adding the manganese acetate, the nickel acetate and the magnesium acetate into the ethylene glycol, adding 0.3mol of potassium carbonate into the ethylene glycol, rotating the speed at 1000rpm, and stirring the mixture for 8 hours;
secondly, putting the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out solvothermal reaction for 10 hours at 130 ℃;
thirdly, annealing the obtained material in a muffle furnace, keeping the temperature at 600 ℃ for 10 hours, and obtaining a target material K after suction filtration, cleaning, drying and grinding 0.6 (NiFeMg) 0.05 Mn 0.7 O 2 。
EXAMPLE 8 Sol-gel Process
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
the first step is as follows: weighing 60ml of ethylene glycol, placing the ethylene glycol in a beaker, weighing 0.7mol of manganese oxalate, 0.05mol of nickel sulfate, 0.05mol of ferrous chloride, 0.05mol of magnesium acetate and 0.3mol of citric acid, adding the mixture into the ethylene glycol, adding 0.3mol of potassium carbonate into the ethylene glycol, rotating at 1000rpm, and stirring for 3 hours;
the second step: putting the mixed solution into a polytetrafluoroethylene reaction kettle, carrying out solvothermal reaction for 6 hours at 150 ℃, and then washing and drying a product;
the third step: annealing the obtained material in a muffle furnace, keeping the temperature at 600 ℃ for 10h, and grinding to obtain a target material K 0.6 (NiFeMg) 0.05 Mn 0.7 O 2 。
Example 9 lyophilization
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
firstly, weighing 0.7mol of manganese oxalate, 0.05mol of nickel sulfate, 0.05mol of ferrous chloride, 0.05mol of magnesium acetate and 0.35mol of potassium carbonate, adding into a centrifuge tube, and then adding 30mL of ultrapure water;
secondly, putting the centrifugal tube into liquid nitrogen for freezing for 0.5h, and then drying the centrifugal tube in a freeze dryer for 48 h;
thirdly, reacting the obtained material in PECVD (plasma enhanced chemical vapor deposition), keeping the reaction at 600 ℃ for 10h, and performing heat treatment to obtain a target material K 0.7 (NiFeMg) 0.05 Mn 0.7 O 2 。
Example 10 coprecipitation method
A preparation method of a high-entropy-like multi-element layered transition metal oxide cathode material comprises the following steps:
the first step is as follows: weighing 0.7mol of manganese oxalate, 0.05mol of nickel sulfate, 0.05mol of ferrous chloride, 0.05mol of magnesium acetate and 0.05mol of aluminum nitrate, adding into a beaker, and adding 30ml of ultrapure water for dissolving;
the second step is that: dropwise adding the obtained transition metal compound mixed solution into 2-15mol/L potassium hydroxide solution, stirring for 5-24 h at the rotation speed of 1000-1500 rpm, sequentially performing suction filtration and cleaning three times by using water and ethanol, drying to obtain a corresponding transition metal hydroxide precursor, and uniformly mixing the dried precipitate with 0.3mol of potassium carbonate;
the third step: annealing the obtained mixture in PECVD (plasma enhanced chemical vapor deposition), keeping the mixture at 600 ℃ for 10h, and grinding the mixture to obtain a target material K 0.6 (NiFeMgAl) 0.05 Mn 0.7 O 2 。
In conclusion, the high-entropy multi-element layered transition metal oxide anode energy storage material is prepared by compounding at least five transition metal elements, a large amount of lattice distortion and a high entropy value exist in the material, structural collapse caused by volume change in the charge and discharge process can be inhibited, the advantages of various elements can be fully exerted in the charge and discharge process, the defects of other elements are inhibited, namely excellent potassium storage, sodium storage and lithium storage performances are realized under the synergistic effect, and the high-entropy multi-element layered transition metal oxide anode energy storage material has the performance characteristics of capacity, multiplying power and cycling stability.
Claims (8)
1. The high-entropy-like multi-element layered transition metal oxide anode material is characterized in that the general formula of the high-entropy-like multi-element anode energy storage material is shown asA x (M) y N z O 2 The general formula is shown in the specification, wherein,Ais a unit of-K, Na, or Li in one or a combination of two equimolar amounts;Mis the combination of at least three equimolar amounts of elements of Ni, Co, Fe, Ti, V, Cr, Zn, Cu, Mg or Al;Nis the combination of one or two of Mn, Mo, W, Bi, Sb, Sn or Te in equal molar quantity, and x is between 0.4 and 1.0, y is between 0.01 and 0.5, and z is between 0.2 and 0.9.
2. The preparation method of the high-entropy-like multi-element layered transition metal oxide cathode material based on claim 1 is characterized by comprising the following steps of: the first step is as follows: according to the general formula of the material design, preparing a uniform composite precursor by performing any one of physical ball milling, freeze drying, solvothermal, sol-gel or coprecipitation on a transition metal compound and an alkali metal compound; and secondly, annealing the precursor to obtain a final product.
3. The preparation method of the high-entropy-like multi-element layered transition metal oxide cathode material as claimed in claim 2, wherein in the first step, the transition metal compound is a transition metal oxide, a transition metal hydroxide, a transition metal carbonate, a transition metal nitrate, a transition metal oxalate, a transition metal sulfate, a transition metal chloride, a transition metal sulfide, a transition metal phosphide or a transition metal nitride.
4. A method for preparing a high-entropy-like multi-layered transition metal oxide positive electrode material as claimed in claim 2, wherein the alkali metal compound in the first step comprises carbonate of lithium, sodium, or potassium, hydroxide of lithium, sodium, or potassium, oxalate of lithium, sodium, or potassium, nitrate of lithium, sodium, or potassium, or sulfate of lithium, sodium, or potassium.
5. The preparation method of the high-entropy-like multi-element layered transition metal oxide cathode material as claimed in claim 2, wherein in the first step, the physical ball milling method comprises the steps of putting a transition metal compound and an alkali metal compound into a ball milling tank, carrying out ball milling for 5-15h, and then washing and drying a product, wherein the ball milling speed is 400-1000 rpm; adding a transition metal compound and an alkali metal compound into a centrifuge tube, adding ultrapure water, transferring into liquid nitrogen for freezing for 0.5h, and drying for 48h by using a freeze dryer; the solvothermal method comprises the steps of uniformly dissolving a transition metal compound in ethylene glycol or an aqueous solution of ethylene glycol, sealing the solution in a solvothermal reaction kettle, carrying out solvothermal reaction at the temperature of 100-220 ℃, wherein the reaction time is 10-20 h, carrying out suction filtration, cleaning, drying and grinding after the reaction is finished, and mixing a solvothermal reaction product with an alkali metal compound to obtain a uniform mixture.
6. The preparation method of the high-entropy-like multi-layered transition metal oxide cathode material as claimed in claim 2, wherein the sol-gel method comprises adding a transition metal compound, citric acid and an alkali metal compound into ethylene glycol, stirring for 3 h, performing a solvothermal reaction at 130-150 ℃ for 6h, and drying the product, wherein the molar amounts of the citric acid and the alkali metal compound are both 2 times that of the transition metal compound; the coprecipitation method comprises the steps of dissolving a transition metal compound in ultrapure water, dropwise adding the solution into 2-15mol/L alkali metal hydroxide solution, stirring at the rotation speed of 1000-1500 rpm for 5-24 h, sequentially and respectively carrying out suction filtration and cleaning with water and ethanol for three times, drying to obtain a corresponding transition metal hydroxide precursor, and then uniformly mixing the dried precipitate product with the alkali metal compound.
7. The preparation method of the high-entropy-like multi-element layered transition metal oxide positive electrode material as claimed in claim 2, wherein the annealing treatment in the second step is specifically: and placing the precursor in a muffle furnace or an oxygen plasma enhanced sintering furnace, annealing at the temperature of 450-1000 ℃ for 0.5-48h, and cooling to room temperature along with the furnace.
8. Use of a high-entropy multi-element layered transition metal oxide positive electrode material of any kind as defined in claims 1 to 7 for the preparation of a positive electrode for a lithium, sodium or potassium ion battery.
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| CN115872462A (en) * | 2023-01-04 | 2023-03-31 | 中国地质大学（北京） | Preparation method of high-entropy oxide positive electrode material of potassium ion battery |
| 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 |
| CN116354407A (en) * | 2023-03-20 | 2023-06-30 | 南京航空航天大学 | High-entropy oxide and preparation method and application thereof |
| CN117334892A (en) * | 2023-09-07 | 2024-01-02 | 南京大学 | Manganese-based layered high-entropy oxide positive electrode material and preparation method thereof |
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| 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 |
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| CN116354407A (en) * | 2023-03-20 | 2023-06-30 | 南京航空航天大学 | High-entropy oxide and preparation method and application thereof |
| CN117334892A (en) * | 2023-09-07 | 2024-01-02 | 南京大学 | Manganese-based layered high-entropy oxide positive electrode material and preparation method thereof |
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