CN111864200B - High-capacity sodium ion battery positive electrode material - Google Patents

High-capacity sodium ion battery positive electrode material Download PDF

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CN111864200B
CN111864200B CN202010866695.7A CN202010866695A CN111864200B CN 111864200 B CN111864200 B CN 111864200B CN 202010866695 A CN202010866695 A CN 202010866695A CN 111864200 B CN111864200 B CN 111864200B
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sodium
positive electrode
ion battery
electrolyte
capacity
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CN111864200A (en
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李福军
王晨晨
刘彦辰
张�林
陈军
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Nankai University
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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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A high-capacity positive electrode material of sodium ion battery. Aiming at the problem of low capacity of the anode material of the existing sodium-ion battery, the invention adopts potassium or lithium doping to obtain a high-capacity layered oxide NaxAyMnzO2(x is more than 0 and less than or equal to 0.67, y is more than or equal to 0 and less than or equal to 0.20, z is more than or equal to 0.80 and less than or equal to 1.00, and A is K or Li) as the anode active material. The invention adds potassium or lithium into the layered manganese-based oxide by a solid-phase synthesis method, thereby greatly improving the charge and discharge capacity of the material. In the system, P2 or P'2 type NaxAyMnzO2When the material is used as a positive electrode material, the reversible specific capacity can reach 248.9mAh/g and 225.4mAh/g under the current densities of 50mA/g and 20 mA/g. The sodium ion battery anode material provided by the invention has the advantages of low preparation cost, high sodium storage capacity and long cycle life, and is expected to be applied to large-scale energy storage.

Description

High-capacity sodium ion battery positive electrode material
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a high-capacity potassium/lithium-doped layered oxide sodium ion battery anode material.
Background
In recent years, sodium ion batteries are widely concerned about abundant sodium resource reserves (the content of sodium in earth crust is 2.64%) and low price, so that the problem of lithium resource shortage is expected to be solved, and the application of the lithium ion batteries in electronic equipment and large-scale energy storage fields is gradually replaced.
However, sodium ion batteries still need to solve a series of problems in practical application. Due to the larger radius of sodium ion
Figure BDA0002649934310000011
Figure BDA0002649934310000012
Therefore, it is difficult to find a suitable material having a high electrochemical activity and reversible sodium deintercalation capacity. In the positive electrode material, layered transition metal oxides, polyanionic compounds, prussian blue compounds, partial organic compounds and the like have been proved to have certain sodium storage capacity and reversible electrochemical behavior. The transition metal oxide has low raw material price and simple preparation process, has a special layered structure and higher sodium storage activity, and is a positive electrode material with a good application prospect. Although the layered transition metal oxide has the advantages, the charge-discharge capacity of the layered transition metal oxide is still low, and the improvement of the energy density of the sodium ion battery is severely limited. On the other hand, the layered structure of the transition metal oxide is changed by the intercalation of sodium ions during the charge and discharge processes, and the severe phase change will cause the attenuation of capacity and voltage. Therefore, the preparation of the cathode material with high capacity and stable cycle has important significance for improving the energy density and the reversibility of the sodium-ion battery, and further promotes the industrial development of the sodium-ion battery.
Disclosure of Invention
The invention aims to solve the problem of low capacity of the conventional positive electrode material of the sodium-ion battery, provide a high-capacity positive electrode material of the sodium-ion battery and improve the sodium storage capacity of the positive electrode material of the sodium-ion battery.
The technical scheme of the invention is as follows:
the positive electrode material of the sodium-ion battery with high capacity comprises the following substances in percentage by mass: 20 to 95 percent of NaxAyMnzO2X is more than 0 and less than or equal to 0.67, y is more than or equal to 0 and less than or equal to 0.20, z is more than or equal to 0.80 and less than or equal to 1.00, A is K or Li, 2-50% of conductive carbon black and 3-50% of polyvinylidene fluoride.
The assembled sodium ion battery comprises a negative pole piece, a positive pole piece, electrolyte, a diaphragm and the like; the negative plate is made of metal sodium. The positive pole piece consists of a current collector and the positive pole material coated on the current collector; the electrolyte includes an organic solvent and a sodium salt.
Preferably, the positive electrode current collector is made of aluminum foil.
Preferably, the organic solvent in the electrolyte is any one of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, propylene carbonate, ethylene carbonate or fluoroethylene carbonate or any combination thereof.
Preferably, the sodium salt in the electrolyte is any one of sodium trifluoromethanesulfonate, sodium hexafluorophosphate, sodium perchlorate, sodium nitrate, sodium bistrifluoromethanesulfonylimide and sodium fluoroborate, or any combination thereof.
Preferably, the concentration of the sodium salt in the electrolyte is 0.1mol/L to 10 mol/L.
The preparation method of the electrolyte comprises the steps of mixing the sodium salt and the organic solvent according to the proportion, and uniformly stirring. Before use, the sodium salt is preferably treated for 10-20 hours in a vacuum oven at 100-120 ℃ to remove water in the raw materials. The organic solvent is preferably used after vacuum distillation and molecular sieve drying and water removal. The electrolyte is preferably used after further water removal through a molecular sieve.
Preferably, the electrolyte further comprises fluoroethylene carbonate serving as other functional additives.
Preferably, the positive electrode active material Na in the positive electrode platexAyMnzO2The loading amount of (A) is 0.5-20 g cm-2。
The positive electrode material Na used in the present inventionxAyMnzO2Reversible sodium storage capacities of up to 248.9 and 225.4mAh/g were obtained when x is 0.10/0.05.
The invention has the advantages and beneficial effects that:
the invention provides a sodium ion battery anode material and a preparation method thereof, wherein the anode material Na is prepared by a solid-phase synthesis methodxAyMnzO2. The sodium ion battery prepared by the anode material provided by the invention greatly improves the charge-discharge specific capacity and the cycling stability, thereby improving the energy density of the sodium ion batteryDegree and cycle life.
Drawings
FIG. 1 shows a positive electrode material Na obtained in example 20.57K0.10MnO2XRD pattern of (a);
FIG. 2 shows a positive electrode material Na obtained in example 50.67Li0.05Mn0.95O2XRD pattern of (a);
FIG. 3 shows a positive electrode material Na obtained in example 20.57K0.10MnO2SEM picture of (1);
FIG. 4 shows a positive electrode material Na obtained in example 50.67Li0.05Mn0.95O2SEM picture of (g);
FIG. 5 is a charge-discharge curve diagram of the sodium ion battery obtained in example 1 (active material loading amount: 1 mg/cm)2Current density: 50 mA/g);
FIG. 6 is a charge-discharge curve diagram of the sodium ion battery obtained in example 2 (active material loading amount: 1 mg/cm)2Current density: 50 mA/g);
FIG. 7 is a charge-discharge curve diagram of the sodium ion battery obtained in example 3 (active material loading amount: 1 mg/cm)2Current density: 50 mA/g);
FIG. 8 is a charge/discharge curve of the sodium ion battery obtained in example 4 (active material loading amount: 2 mg/cm)2Current density: 50 mA/g);
FIG. 9 is a charge/discharge curve of the sodium ion battery obtained in example 5 (active material loading amount: 1 mg/cm)2Current density: 20 mA/g);
FIG. 10 is a charge/discharge curve of the sodium ion battery obtained in example 6 (active material loading amount: 1 mg/cm)2Current density: 20 mA/g;
FIG. 11 is a charge/discharge curve of the sodium ion battery obtained in example 7 (active material loading amount: 1 mg/cm)2Current density: 20 mA/g).
FIG. 12 is a charge/discharge curve of the sodium ion battery obtained in example 8 (active material loading amount: 2 mg/cm)2Current density: 20 mA/g).
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings.
The purity of sodium carbonate, potassium carbonate, lithium carbonate, manganese oxide, organic solvent, metallic sodium and sodium salt used in the examples is not less than 99%.
Example 1:
this example provides a positive electrode material of sodium ion battery, which is P2 phase layered oxide Na0.64K0.03MnO2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100 percent) is as follows: 70% of Na0.64K0.03 MnO 220% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.64K0.03MnO2The specific synthesis method comprises the following steps:
adopting a sol-gel method, uniformly mixing 14.08mmol of sodium acetate, 0.66mmol of potassium carbonate and 20.00mmol of manganese sesquioxide, placing the mixture into a ball milling tank, adding 4mL of acetone, carrying out ball milling for 12h under the condition of 400r/min, drying the product in a forced air oven at 120 ℃ for 12h, drying the acetone by distillation, grinding the acetone, tabletting the acetone by an infrared die, roasting the product for 15h at 900 ℃, cooling and quickly placing the product into an argon atmosphere glove box.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: propylene carbonate.
The electrolyte salt is: sodium hexafluorophosphate, the amount concentration of its substance in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the formula of the positive electrode material, mixing the positive electrode material with a conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying the aluminum foil for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.6795g of sodium hexafluorophosphate, 10mL of propylene carbonate and 0.4124g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, were assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.3V.
FIG. 5 shows P2 phase Na0.64K0.03MnO2The charge-discharge curve chart shows that the current density is 50mA/g, the first-circle charging specific capacity is 115.3mAh/g, and the first-circle discharging specific capacity is 205.9mAh/g, so that the excellent sodium storage performance is shown.
Example 2:
this example provides a positive electrode material of sodium ion battery, which is P2 phase layered oxide Na0.57K0.10MnO2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100 percent) is as follows: 70% of Na0.57K0.10MnO220% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.57K0.10MnO2The specific synthesis method comprises the following steps:
adopting a sol-gel method, uniformly mixing 12.54mmol of sodium acetate, 2.20mmol of potassium carbonate and 20.00mmol of manganese sesquioxide, placing the mixture into a ball milling tank, adding 4mL of acetone, carrying out ball milling for 12h under the condition of 400r/min, drying the product in an air-blowing oven at 120 ℃ for 12h, drying the acetone by distillation, grinding, tabletting by using an infrared die, roasting for 15h under the condition of 900 ℃, cooling, and quickly placing the product into an argon atmosphere glove box.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: propylene carbonate.
The electrolyte salt is: sodium hexafluorophosphate, the amount concentration of its substance in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the formula of the positive electrode material, mixing the positive electrode material with a conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in an N-methyl-2-pyrrolidone (NMP) solution to prepare a mixed slurry of the positive electrode, coating the slurry on an aluminum foil of a positive current collector, drying the aluminum foil for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.6795g of sodium hexafluorophosphate, 10mL of propylene carbonate and 0.4124g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, were assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.3V.
FIG. 1 shows P2 phase Na0.57K0.10MnO2XRD pattern of (a); FIG. 3 is Na0.57K0.10MnO2SEM image of (5) sample is 5 μm block-shaped particles; FIG. 6 is a charge-discharge curve diagram, wherein the current density is 50mA/g, the first-turn specific charge capacity is 194.3mAh/g, and the first-turn specific discharge capacity is 250.0mAh/g, showing excellent sodium storage performance.
Example 3:
this example provides a positive electrode material of sodium ion battery, which is P2 phase layered oxide Na0.47K0.20MnO2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100 percent) is as follows: 70% of Na0.47K0.20MnO220% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.47K0.20MnO2The specific synthesis method comprises the following steps:
adopting a sol-gel method, uniformly mixing 10.34mmol of sodium acetate, 4.40mmol of potassium carbonate and 20.00mmol of manganese sesquioxide, placing the mixture into a ball milling tank, adding 4mL of acetone, carrying out ball milling for 12h under the condition of 400r/min, drying the product in a forced air oven at 120 ℃ for 12h, drying the acetone by distillation, grinding the acetone, tabletting the acetone by an infrared die, roasting the product for 15h at 900 ℃, cooling and quickly placing the product into an argon atmosphere glove box.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: propylene carbonate.
The electrolyte salt is: sodium hexafluorophosphate, the amount concentration of its substance in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, mixing the positive electrode material with the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.6795g of sodium hexafluorophosphate, 10mL of propylene carbonate and 0.4124g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, are assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.3V.
FIG. 7 shows P2 phase Na0.47K0.20MnO2The charge-discharge curve chart shows that the current density is 50mA/g, the first-circle charging specific capacity is 155.7mAh/g, and the first-circle discharging specific capacity is 249.7mAh/g, so that the excellent sodium storage performance is shown.
Example 4:
this example provides a positive electrode material of sodium ion battery, which is P2 phase layered oxide Na0.57K0.10MnO2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100 percent) is as follows: 80% of Na0.57K0.10MnO210% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.57K0.10MnO2The specific synthesis method comprises the following steps:
adopting a sol-gel method, uniformly mixing 12.54mmol of sodium acetate, 2.20mmol of potassium carbonate and 20.00mmol of manganese sesquioxide, placing the mixture into a ball milling tank, adding 4mL of acetone, carrying out ball milling for 12h under the condition of 400r/min, drying the product in an air-blowing oven at 120 ℃ for 12h, drying the acetone by distillation, grinding, tabletting by using an infrared die, roasting for 15h under the condition of 900 ℃, cooling, and quickly placing the product into an argon atmosphere glove box.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: propylene carbonate.
The electrolyte salt is: sodium hexafluorophosphate, the substance amount concentration of which in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the formula of the positive electrode material, mixing the positive electrode material with a conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in an N-methyl-2-pyrrolidone (NMP) solution to prepare a mixed slurry of the positive electrode, coating the slurry on an aluminum foil of a positive current collector, drying the aluminum foil for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.6795g of sodium hexafluorophosphate, 10mL of propylene carbonate and 0.4124g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, were assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.3V.
FIG. 1 shows P2 phase Na0.57K0.10MnO2XRD pattern of (a); FIG. 3 is Na0.57K0.10MnO2SEM image of (5) sample is 5 μm block-shaped particles; FIG. 8 is a charge-discharge curve diagram, wherein the current density is 50mA/g, the first-turn charging specific capacity is 132.1mAh/g, and the first-turn discharging specific capacity is 239.2mAh/g, showing excellent sodium storage performance.
Example 5:
this example provides a positive electrode material of sodium ion battery, which is P'2 phase layered oxide Na0.67Li0.03Mn0.97O2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100%): 70% of Na0.67Li0.03Mn0.97O220% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.67Li0.03Mn0.97O2The specific synthesis method comprises the following steps:
by adopting a high-temperature solid phase method, 10.56mmol of sodium carbonate, 0.48mmol of lithium carbonate and 14.54mmol of manganese sesquioxide are uniformly mixed and then placed in a ball milling tank, 4mL of acetone is added, ball milling is carried out for 12h under the condition of 400r/min, the product is dried for 12h in an air-blast oven at 120 ℃, the acetone is evaporated to dryness and then ground, the mixture is tabletted by an infrared die, roasted for 15h at 1000 ℃, and the mixture is quickly placed in an argon atmosphere glove box after quenching in air.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: ethylene carbonate and propylene carbonate in a volume ratio of 1: 1.
The electrolyte salt is: sodium perchlorate, the mass concentration of which in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, mixing the positive electrode material with the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.2244g of sodium perchlorate, 5mL of propylene carbonate, 6.609g of ethylene carbonate and 0.6928g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, are assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.4V.
FIG. 9 shows P'2 phase Na0.67Li0.03Mn0.97O2Charge-discharge curve diagram of (1), current densityThe degree is 20mA/g, the charging specific capacity of the first circle is 149.7mAh/g, the discharging specific capacity of the first circle is 201.7mAh/g, and the excellent sodium storage performance is shown.
Example 6:
this example provides a positive electrode material of sodium ion battery, which is P'2 phase layered oxide Na0.67Li0.05Mn0.95O2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100 percent) is as follows: 70% of Na0.67Li0.05Mn0.95O220% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.67Li0.05Mn0.95O2The specific synthesis method comprises the following steps:
by adopting a high-temperature solid phase method, 10.56mmol of sodium carbonate, 0.79mmol of lithium carbonate and 14.24mmol of manganese sesquioxide are uniformly mixed and then placed in a ball milling tank, 4mL of acetone is added, ball milling is carried out for 12h under the condition of 400r/min, the product is dried for 12h in a forced air oven at 120 ℃, the acetone is dried and ground after being evaporated to dryness, the product is pressed into sheets by an infrared die, roasted for 15h under the condition of 1000 ℃, and the sheets are quickly placed in an argon atmosphere glove box after being quenched in air.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: ethylene carbonate and propylene carbonate in a volume ratio of 1: 1.
The electrolyte salt is: sodium perchlorate, the mass concentration of which in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, mixing the positive electrode material with the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.2244g of sodium perchlorate, 5mL of propylene carbonate, 6.609g of ethylene carbonate and 0.6928g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, were assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.4V.
FIG. 2 shows P'2 phase Na0.67Li0.05Mn0.95O2XRD pattern of (a); FIG. 4 shows Na0.67Li0.05Mn0.95O2SEM image of (5) sample is 5 μm block-shaped particles; FIG. 10 is a charge-discharge curve diagram, wherein the current density is 20mA/g, the first-turn specific charge capacity is 139.1mAh/g, and the first-turn specific discharge capacity is 225.4mAh/g, showing excellent sodium storage performance.
Example 7:
the embodiment provides a positive electrode material of a sodium ion battery and assembles the sodium ion battery, wherein the positive electrode active material is P'2 phase layered oxide Na0.67Li0.15Mn0.85O2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100%): 70% of Na0.67Li0.15Mn0.85O220% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.67Li0.15Mn0.85O2The specific synthesis method comprises the following steps:
by adopting a high-temperature solid phase method, 10.56mmol of sodium carbonate, 2.37mmol of lithium carbonate and 12.74mmol of manganese sesquioxide are uniformly mixed and then placed in a ball milling tank, 4mL of acetone is added, ball milling is carried out for 12h under the condition of 400r/min, the product is dried for 12h in a forced air oven at 120 ℃, the acetone is evaporated to dryness and then ground, the mixture is pressed into sheets by an infrared die, roasted for 15h under the condition of 1000 ℃, and the sheets are quickly placed in an argon atmosphere glove box after quenching in air.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: ethylene carbonate and propylene carbonate in a volume ratio of 1: 1.
The electrolyte salt is: sodium perchlorate, the mass concentration of which in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, mixing the positive electrode material with the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.2244g of sodium perchlorate, 5mL of propylene carbonate, 6.609g of ethylene carbonate and 0.6928g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, were assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.4V.
FIG. 11 shows P'2 phase Na0.67Li0.15Mn0.85O2The charge-discharge curve chart shows that the current density is 20mA/g, the first-circle charging specific capacity is 122.3mAh/g, and the first-circle discharging specific capacity is 147.2mAh/g, so that the excellent sodium storage performance is shown.
Example 8:
this example provides a positive electrode material of sodium ion battery, which is P'2 phase layered oxide Na0.67Li0.05Mn0.95O2。
The composition of the positive electrode material of the sodium-ion battery (based on the mass fraction of the positive electrode material as 100 percent) is as follows: 80% of Na0.67Li0.05Mn0.95O210% of conductive carbon black and 10% of polyvinylidene fluoride.
The Na is0.67Li0.05Mn0.95O2The specific synthesis method comprises the following steps:
by adopting a high-temperature solid phase method, 10.56mmol of sodium carbonate, 0.79mmol of lithium carbonate and 14.24mmol of manganese sesquioxide are uniformly mixed and then placed in a ball milling tank, 4mL of acetone is added, ball milling is carried out for 12h under the condition of 400r/min, the product is dried for 12h in a forced air oven at 120 ℃, the acetone is dried and ground after being evaporated to dryness, the product is pressed into sheets by an infrared die, roasted for 15h under the condition of 1000 ℃, and the sheets are quickly placed in an argon atmosphere glove box after being quenched in air.
The counter electrode of the sodium ion battery is metallic sodium.
The solvent of the electrolyte is: ethylene carbonate and propylene carbonate in a volume ratio of 1: 1.
The electrolyte salt is: sodium perchlorate, the mass concentration of which in the electrolyte is 1.0mol/L.
Electrolyte additive: fluoroethylene carbonate, the mass ratio of which in the electrolyte is 5%.
The preparation method of the battery comprises the following steps:
preparing a positive electrode: weighing the raw materials according to the positive electrode formula, mixing the positive electrode material with the conductive agent, grinding polyvinylidene fluoride, uniformly dispersing the mixture in N-methyl-2-pyrrolidone (NMP) solution to prepare mixed slurry of the positive electrode, coating the slurry on a positive electrode current collector aluminum foil, drying for 10 hours at 80 ℃ in a vacuum drying oven, and slicing to obtain the positive electrode piece.
Preparing an electrolyte: 1.2244g of sodium perchlorate, 5mL of propylene carbonate, 6.609g of ethylene carbonate and 0.6928g of fluoroethylene carbonate are weighed by an electronic balance in a glove box filled with high-purity argon, stirred uniformly and then kept stand for 12 hours to prepare the electrolyte.
The sodium sheet, electrolyte and positive electrode sheet of the sodium ion battery prepared above, and other necessary battery components, for example, a separator (Glass fiber) and a case, were assembled into a 2032 type coin cell.
The battery prepared in this example was subjected to a charge-discharge capacity test: and (3) carrying out constant-current charge and discharge tests by using a Land CT2001A battery test system at normal temperature, wherein the test voltage interval is 1.8V-4.4V.
FIG. 2 shows P'2 phase Na0.67Li0.05Mn0.95O2XRD pattern of (a); FIG. 4 shows Na0.67Li0.05Mn0.95O2SEM image of (5) sample is 5 μm block-shaped particles; FIG. 12 is a charge-discharge curve diagram, wherein the current density is 20mA/g, the first-turn specific charge capacity is 136.8mAh/g, and the first-turn specific discharge capacity is 192.2mAh/g, showing excellent sodium storage performance.

Claims (1)

1. The positive electrode material of the sodium-ion battery with high capacity comprises the following substances in percentage by mass: 20% -95% of NaxAyMnzO2X is more than 0 and less than or equal to 0.67, y is more than or equal to 0 and less than or equal to 0.20, z is more than or equal to 0.80 and less than or equal to 1.00, A is K of P2 phase or Li of P'2 phase, 2-50% of conductive carbon black and 3-50% of polyvinylidene fluoride.
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