CN112002886A - Potassium ion battery negative electrode material metal alloy and preparation method thereof - Google Patents
Potassium ion battery negative electrode material metal alloy and preparation method thereof Download PDFInfo
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Abstract
The chemical general formula of the metal alloy is M1‑xNx@ C, wherein, 0<x<0.5, M is one of metals Sb and Bi, and N is one of metals Fe, Cu, Co, Ni and Zn. The invention also comprises a preparation method of the metal alloy of the negative electrode material of the potassium ion battery, which is characterized in that: dissolving metal salt and organic ligand according to a certain proportion, heating the solvent to obtain bimetallic MOF, and putting the bimetallic MOF in argon-hydrogen atmosphere for pyrolysis to obtainTo carbon clad bimetallic alloys. The metal organic framework is used as a precursor, and the carbon-coated bimetallic alloy negative electrode material is prepared by a pyrolysis method. The invention has simple process and easy repetition, and is beneficial to realizing the large-range application of the materials.
Description
Technical Field
The invention belongs to the field of potassium ion battery cathode materials, and particularly relates to a metal alloy and a preparation method thereof.
Background
The scarcity and uneven distribution of lithium resources and the increasing lithium consumption year by year lead to the higher price of Lithium Ion Batteries (LIBs), and limit the application of LIBs in large-scale energy storage systems such as smart grids and the like. Among alkali metal elements, K is abundant, widely distributed and low in price in the earth crust, and has similar physicochemical properties to Li+Standard electrode potential of/K with Li+Similar to Li, the advantages enable the potassium ion batteries (KIBs) to be expected to be applied to the field of large-scale energy storage. The development of electrode materials is the key of the development of novel batteries, wherein the cycle stability and high rate performance of the negative electrode material are one of the key factors of commercial popularization and application of potassium ion batteries.
According to the potassium storage mechanism of electrode materials, potassium ion battery cathode materials are mainly divided into de-intercalation materials, alloy materials and conversion materials. The cathode material of the deintercalation type potassium ion battery mainly comprises a carbon material and a titanium-based material, and comprises a graphite-based carbon material, amorphous carbon and titanate. Although the crystal structure of the material is relatively stable, potassium ions can be rapidly diffused among crystal lattices of the material, the theoretical specific capacity of the material is not high, and the development of the material is limited. Compared with an embedded material, the alloy material can provide higher potassium ion storage capacity, is safe and reliable, has wide resources and low raw material price, is a powerful competitor of a new generation of power battery cathode material, draws attention of people, and particularly relates to the alloy electrode material. However, the conventional alloy battery material has high synthesis temperature, and the uniformity of the multi-phase alloy cannot be ensured, so that the effective application of the alloy material is inhibited. As in application No. 200610012198.0
In conclusion, the carbon-coated metal alloy with good conductivity and cycle performance is prepared by taking the metal organic framework as a precursor and utilizing a simple pyrolysis method.
Disclosure of Invention
The invention aims to solve the technical problem that a carbon-coated metal alloy with good conductivity and cycle performance is prepared by using a simple solvothermal-pyrolysis method and using a metal organic framework material as a precursor.
The technical scheme adopted by the invention for solving the technical problems is as follows: metal alloy of negative electrode material of potassium ion battery, M1- xNx@ C, wherein, 0<x<0.5, wherein M is one of metals Sb and Bi, and N is one of metals Fe, Cu, Co, Ni and Zn.
The preparation method of the metal alloy of the potassium ion battery negative electrode material comprises the following steps:
(1) dissolving two metal salts in a certain proportion in a certain volume of a solvent A1 to obtain a solution B1 with a certain concentration, dispersing a certain amount of carbon source in a certain volume of a solvent A2 to obtain a dispersion B2 with a certain concentration, dissolving a certain amount of organic ligand in the dispersion B2 to obtain a solution B3, pouring the solution B3 into the solution B1, carrying out solvothermal reaction for a certain time at a certain temperature, centrifuging, washing, and freeze-drying to obtain a metal organic framework precursor, wherein the molar ratio of the organic ligand to the metal nitrate is W;
(2) carrying out heat treatment on a certain amount of metal organic framework precursor at a certain temperature for a certain time under an inert atmosphere to obtain a metal alloy;
further, in the step (1), the metal salt is one or a mixture of several of nitrate, acetate and acetylacetone salt;
further, in the step (1), the solvent A1 is one or a mixture of methanol, ethanol, ethylene glycol, N, N-dimethylformamide and N-methylpyrrolidone;
further, in the step (1), the concentration of the total metal solution in the solution B1 is 0.005-2 mol/L;
further, in the step (1), the solvent A2 is one or a mixture of more of ethylene glycol, N-methylpyrrolidone and N-N dimethylformamide;
further, in the step (1), the concentration of the carbon source in the solution B2 is 0.01-10 mg/mL;
further, in the step (1), the concentration of the organic ligand in the solution B3 is 0.01-5 mol/L;
further, in the step (1), the solvothermal reaction time is 1-30 h;
further, in the step (1), the reaction temperature is 120-220 ℃;
further, in the step (1), the organic ligand is trimesic acid or terephthalic acid, and the molar ratio W of the organic ligand to the metal salt is 1-100: 1;
further, in the step (1), the carbon source is graphene oxide or carbon nano tubes, and the mass of the carbon source is 5-20% of the mass of a theoretical product;
further, in the step (2), the heat treatment temperature is 400-1000 ℃;
further, in the step (2), the heat treatment time is 30min-10 h.
Further, in the step (2), the inert atmosphere is one or a mixture of more of high-purity nitrogen, high-purity argon, a mixed gas of hydrogen and nitrogen containing 1% -10% of hydrogen, and a mixed gas of hydrogen and argon containing 1% -10% of hydrogen;
the invention has the beneficial effects that: the metal alloy is prepared by a solvothermal-pyrolysis method, and the scheme is simple and convenient to operate, easy to repeat and beneficial to large-scale popularization and application.
Drawings
FIG. 1 is an SEM photograph of a product prepared in example 2 of the present invention;
FIG. 2 is a graph of the cycle performance of the product produced in example 2 of the present invention;
FIG. 3 is an SEM photograph of the product prepared in example 6 of the present invention;
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Weighing 4mmol of bismuth nitrate and 0.5mmol of copper nitrate, dissolving in 100mL of methanol, weighing 10mg of graphene oxide, dispersing in 100mL of methanol, dissolving 4mmol of trimesic acid in graphene oxide dispersion liquid after full dispersion, pouring the dispersion liquid into a metal salt solution, fully mixing, transferring into a solvothermal kettle, carrying out solvothermal reaction at 180 ℃ for 24 hours, and obtaining a precursor after centrifugation, washing and freeze drying;
(2) weighing 2mmol of precursor, placing the precursor in a magnetic boat, and keeping the temperature of 600 ℃ for 2 hours under the atmosphere of high-purity argon to obtain bismuth-copper alloy;
(3) weighing 0.07g of the prepared alloy, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, bonding agent), fully grinding, adding 0.4mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (Kevlar-Powerk) as a KPF (Kevlar-Powerk-Verwen) electrode6The solution (solvent EC: DEC, volume ratio 1: 1) was used as electrolyte, and glass fiber membrane (GF/D, Whatman) was used as separator to assemble CR2032 type button cell. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power, the initial specific discharge capacity of the alloy material is 676.3mA h g-1The first charge capacity is 608.3mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 0.5C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 225.7mA hr g-1。
Example 2
(1) Weighing 4mmol of bismuth nitrate and 2mmol of ferric nitrate, dissolving in 100mL of ethylene glycol, weighing 10mg of graphene oxide, dispersing in 100mL of ethylene glycol, fully dispersing, dissolving 4mmol of trimesic acid in graphene oxide dispersion liquid, pouring the dispersion liquid into a metal salt solution, fully mixing, transferring into a solvothermal kettle, carrying out solvothermal reaction at 180 ℃ for 24 hours, centrifuging, washing, and freeze-drying to obtain a precursor;
(2) weighing 2mmol of precursor, placing the precursor in a magnetic boat, and keeping the temperature of 600 ℃ for 2 hours under the atmosphere of high-purity argon to obtain bismuth-iron alloy;
(3) weighing 0.07g of the prepared alloy, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, bonding agent), fully grinding, adding 0.4mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (Kevlar-Powerk) as a KPF (Kevlar-Powerk-Verwen) electrode6Solution (solvent EC: DEC body)Volume ratio of 1: 1) as electrolyte, and glass fiber membrane (GF/D, Whatman) as diaphragm, to assemble CR2032 type button cell. The bismuth-iron alloy material was found to have a micro-flower morphology of 10-15 μm by scanning electron microscopy analysis (FIG. 1). According to the cyclic performance test (figure 2), when the constant-current charging and discharging test is carried out at 25 ℃ and 0.1C multiplying power between 0.1 and 3.0V, the first discharging specific capacity of the bismuth-iron alloy material is 579.5mA h g-1The first charge capacity is 340.0mA hr g-1. Constant current charge and discharge test is carried out at 25 ℃ and 0.3C multiplying power in a 0.1-3.0V interval, and the specific discharge capacity after 35 cycles is 159.9mA hr g-1。
Example 3
(1) Weighing 3mmol of bismuth nitrate and 1mmol of zinc nitrate, dissolving in 80mL of ethylene glycol, weighing 15mg of graphene oxide, dispersing in 80mL of ethylene glycol, dissolving 3mmol of trimesic acid in graphene oxide dispersion liquid after full dispersion, pouring the dispersion liquid into a metal salt solution, fully mixing, transferring into a solvothermal kettle, carrying out solvothermal reaction for 12 hours at 200 ℃, and obtaining a precursor after centrifugation, washing and freeze drying;
(2) weighing 2mmol of precursor, placing the precursor in a magnetic boat, and keeping the temperature of 700 ℃ for 2 hours under the atmosphere of high-purity argon to obtain bismuth-iron alloy;
(3) weighing 0.07g of the prepared alloy, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, bonding agent), fully grinding, adding 0.4mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (Kevlar-Powerk) as a KPF (Kevlar-Powerk-Verwen) electrode6The solution (EC: DEC in a volume ratio of 1: 1) was used as an electrolyte and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. When constant current charge and discharge test is carried out at 25 ℃ and 0.1-3.0V multiplying power at 0.1C, the first discharge specific capacity of the bismuth-zinc alloy material is 610.5mA h g-1The first charge capacity is 544.2mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 1C rate in 0.1-3.0V interval, and discharging specific capacity of 211.8mA hr g after circulating for 100 circles-1。
Example 4
(1) Weighing antimony acetate 4mmol and ferric acetate 2mmol, dissolving in 100mL of ethylene glycol, weighing graphene oxide 10mg, dispersing in 100mL of ethylene glycol, dissolving trimesic acid 4mmol in graphene oxide dispersion liquid after full dispersion, pouring the graphene oxide dispersion liquid into a metal salt solution, after full mixing, transferring into a solvothermal kettle, carrying out solvothermal reaction for 12h at 200 ℃, and obtaining a precursor after centrifugation, washing and freeze drying;
(2) weighing 2mmol of precursor, placing the precursor in a magnetic boat, and keeping the temperature of 600 ℃ for 2 hours under the atmosphere of high-purity argon to obtain an antimony-iron alloy;
(3) weighing 0.07g of the prepared alloy, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, bonding agent), fully grinding, adding 0.4mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (Kevlar-Powerk) as a KPF (Kevlar-Powerk-Verwen) electrode6The solution (EC: DEC in a volume ratio of 1: 1) was used as an electrolyte and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power at 0.1C, the initial discharge specific capacity of the antimony-iron alloy material is 879.5mA h g-1The first charge capacity is 702.5mA h g-1. Performing constant current charge and discharge test at 25 deg.C and 1C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 363.2mA hr g-1。
Example 5
(1) Weighing antimony nitrate 4mmol and zinc nitrate 2mmol, dissolving in 100mL of ethylene glycol, weighing graphene oxide 10mg, dispersing in 100mL of ethylene glycol, dissolving terephthalic acid 4mmol in graphene oxide dispersion liquid after full dispersion, pouring the graphene oxide dispersion liquid into metal nitrate, fully mixing, transferring into a solvothermal kettle, carrying out solvothermal reaction at 180 ℃ for 24h, centrifuging, washing, and freeze-drying to obtain a precursor;
(2) weighing 2mmol of precursor, placing the precursor in a magnetic boat, and keeping the temperature of 600 ℃ for 2 hours under the atmosphere of high-purity argon to obtain a bismuth-zinc alloy;
(3) weighing 0.07g of the prepared alloy, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, bonding agent), fully grinding, adding 0.4mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (Kevlar-Powerk) as a KPF (Kevlar-Powerk-Verwen) electrode6The solution (EC: DEC in a volume ratio of 1: 1) was used as an electrolyte and a glass fiber membrane (GF/D, Whatman) was used as a separator to assemble a CR2032 type button cell. When constant current charge and discharge test is carried out at 25 ℃ and 0.1-3.0V multiplying power at 0.1C, the first discharge specific capacity of the bismuth-zinc alloy material is 709.2mA h g-1First charge capacity of 634.0mA hr g-1. Performing constant current charge and discharge test at 25 deg.C and 0.5C rate in 0.1-3.0V interval, and discharging specific capacity after 50 weeks circulation is 391.7mA hr g-1。
Example 6
(1) Weighing 4mmol of bismuth nitrate and 0.5mmol of ferric nitrate, dissolving in 50mL of ethylene glycol, weighing 20mg of graphene oxide, dispersing in 100mL of ethylene glycol, dissolving 4mmol of trimesic acid in graphene oxide dispersion liquid after full dispersion, pouring the graphene oxide dispersion liquid into a metal salt solution, fully mixing, transferring into a solvothermal kettle, carrying out solvothermal reaction at 180 ℃ for 24 hours, and obtaining a precursor after centrifugation, washing and freeze drying;
(2) weighing 2mmol of precursor, placing the precursor in a magnetic boat, and keeping the temperature of 600 ℃ for 2 hours under the atmosphere of high-purity argon to obtain bismuth-iron alloy;
(3) weighing 0.07g of the prepared alloy, 0.02g of acetylene black (conductive agent) and 0.01g of PVDF (HSV900, bonding agent), fully grinding, adding 0.4mL of NMP for dispersing and mixing, uniformly mixing, pulling slurry on a copper foil for flaking, blowing air at 80 ℃ for drying, cutting into circular sheets with the diameter of 12mm, assembling in a glove box in argon atmosphere, taking a metal potassium sheet as a counter electrode, and using 1M KPF (Kevlar-Powerk) as a KPF (Kevlar-Powerk-Verwen) electrode6The solution (EC: DEC volume ratio of 1: 1) is used as electrolyte, glass fiber membrane (GF/D, Whatman) is used as diaphragm, and CR2032 type button cell is assembledAnd (4) a pool. The bismuth-iron alloy material is in a micron strip shape of 5-10 mu m through analysis of a scanning electron microscope (figure 3). When constant-current charge and discharge tests are carried out at 25 ℃ and 0.1-3.0V multiplying power, the first discharge specific capacity of the bismuth-iron alloy material is 683.3mA h g-1The first charge capacity is 632.6mA h g-1. Performing constant current charge and discharge test at 25 deg.C under 1C rate in 0.1-3.0V interval, and discharging specific capacity after 50 cycles is 205.7mA hr g-1
The above description is only a basic description of the present invention, and any equivalent changes made according to the technical solution of the present invention should fall within the protection scope of the present invention.
Claims (10)
1. The metal alloy for the negative electrode material of the potassium ion battery is characterized in that: m1-xNx@ C, wherein, 0<x<0.5, wherein M is one of metals Sb and Bi, and N is one of metals Fe, Cu, Co, Ni and Zn.
2. The method for preparing the metal alloy of the negative electrode material of the potassium-ion battery as claimed in claim 1, characterized by comprising the following steps:
(1) dissolving two metal salts in a certain proportion in a certain volume of a solvent A1 to obtain a solution B1 with a certain concentration, dispersing a certain amount of carbon source in a certain volume of a solvent A2 to obtain a dispersion B2 with a certain concentration, dissolving a certain amount of organic ligand in the carbon source dispersion B2 to obtain a solution B3, pouring the solution B3 into the solution B1, carrying out solvothermal reaction for a certain time at a certain temperature, centrifuging, washing, and freeze-drying to obtain a metal organic framework precursor, wherein the molar ratio of the organic ligand to the metal nitrate is W;
(2) and carrying out heat treatment on a certain amount of metal organic framework precursor at a certain temperature for a certain time under an inert atmosphere to obtain the metal alloy.
3. The method for preparing the metal alloy of the negative electrode material of the potassium-ion battery according to claim 2, wherein in the step (1), the solvent A1 is one or more of methanol, ethanol, ethylene glycol, N, N-dimethylformamide and N-methylpyrrolidone; the solvent A2 is one or more of ethylene glycol, N-methyl pyrrolidone and N-N dimethylformamide.
4. The method for preparing the metal alloy for the negative electrode material of the potassium ion battery as claimed in claim 2, wherein in the step (1), the total metal solution concentration of the solution B1 is 0.005-2 mol/L; the carbon source concentration of the dispersion liquid B2 is 0.01-10mg/mL, and the concentration of the organic ligand in the solution B3 is 0.01-5 mol/L.
5. The method for preparing the metal alloy for the negative electrode material of the potassium ion battery as claimed in claim 2, wherein in the step (1), the carbon source is graphene oxide or carbon nanotubes, the organic ligand is one of trimesic acid or terephthalic acid, and the molar ratio W of the organic ligand to the metal salt is 1-100: 1.
6. The method for preparing the metal alloy of the negative electrode material of the potassium-ion battery as claimed in claim 2, wherein the solvothermal reaction temperature in the step (1) is 120-220 ℃.
7. The preparation method of the metal alloy for the negative electrode material of the potassium-ion battery as claimed in claim 2, wherein the solvothermal reaction time in the step (1) is 1h to 30 h.
8. The method for preparing the metal alloy for the negative electrode material of the potassium-ion battery as claimed in claim 2, wherein in the step (1), the mass of the carbon source is 5-20% of the mass of the theoretical product.
9. The method for preparing the metal alloy for the negative electrode material of the potassium-ion battery according to claim 2, wherein the heat treatment temperature in the step (2) is 400-1000 ℃.
10. The method for preparing the metal alloy for the negative electrode material of the potassium-ion battery as claimed in claim 2, wherein the heat treatment time in the step (2) is 30min to 10 h.
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