CN112864389A - Sodium-ion battery positive electrode material and preparation method and application thereof - Google Patents
Sodium-ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a sodium ion battery positive electrode material and a preparation method and application thereof, and belongs to the technical field of sodium ion batteries. The chemical composition of the positive electrode material of the sodium-ion battery is NaxNiyM1‑yO2@ conductive carbon; wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0.1 and less than or equal to 0.5, M is selected from at least one of Mn, Fe, Zn, Ag, Zr, Mo, Nb, Cu, Cr and Ti, and the conductive carbon is selected from at least one of graphene, carbon nanotubes, conductive carbon black and acetylene black; the content of the conductive carbon in the sodium-ion battery positive electrode material is 1-10 wt%; the sodium isThe specific surface area of the positive electrode material of the ion battery is 0.3-1.2 m2(ii)/g; and/or the D50 particle size of the positive electrode material of the sodium-ion battery is 5-30 nm. The positive electrode material of the sodium ion battery is in a nano size, has the advantages of high dispersibility, large specific surface area and the like, is beneficial to improving the cycle performance and rate capability of the material, and can improve the charge-discharge capacity, specific capacity, cycle stability and service life of the sodium ion battery.
Description
Technical Field
The application relates to a sodium ion battery positive electrode material and a preparation method and application thereof, belonging to the technical field of sodium ion batteries.
Background
In the nineties of the twentieth century, among many secondary batteries, lithium ion batteries were the first to take a strong opportunity to develop. According to the statistics data of the energy storage industry technical alliance of Guancun in 2019, the method comprises the following steps: in the global electrochemical scale energy storage demonstration project, the occupancy rate of lithium ion batteries is up to 80%. However, although the performance of the lithium ion battery is good, the reserve of lithium resources is limited, 70% of lithium resources are distributed in south america, and at present, 80% of lithium resources in China depend on import, so that many researchers begin to search for new alternative energy sources.
Sodium is the fourth most abundant element in the world, the price is low, and the sodium ion battery has the advantages of long service life, high safety performance and the like, not only can be supplemented to the lithium ion battery to a certain extent, and relieve the problem of lithium resource shortage, but also can gradually replace the lead-acid battery with serious environmental pollution, and ensure national energy safety and social sustainable development, so that the sodium ion battery becomes a next-generation energy storage device.
In the structural composition of the sodium ion battery, the positive electrode material is used as a main body part of sodium storage and is an important factor for determining the safety performance, the electrochemical performance and the future development of the sodium ion battery, and at present, the positive electrode material of the sodium ion battery is mainly transition metal oxide. When the transition metal oxide containing cobalt is used as a sodium ion anode material, the energy density and the charge and discharge capacity of the battery are favorably improved, but the chemical stability and the safety performance of the battery are reduced due to the existence of cobalt, and the price of cobalt is higher.
In addition, the conventional method for synthesizing the transition metal oxide cathode material mainly comprises a solid phase method, an electrostatic spinning method, a hydrothermal method and the like, the process is complicated, and the external uncontrollable factors are more.
Disclosure of Invention
In order to solve the problems, the positive electrode material of the sodium ion battery is nano-sized, has the advantages of high dispersibility, large specific surface area and the like, is convenient for the rapid transfer of sodium ions and electrons in a material body phase, is beneficial to improving the cycle performance and rate capability of the material, and can improve the charge-discharge capacity, specific capacity, cycle stability and service life of the sodium ion battery; in addition, the cathode material does not contain cobalt, and has the advantages of good chemical stability, excellent safety performance and low price.
According to one aspect of the application, a positive electrode material of a sodium-ion battery is provided, and the chemical composition of the positive electrode material of the sodium-ion battery is NaxNiyM1-yO2@ conductive carbon;
wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0.1 and less than or equal to 0.5, M is selected from at least one of Mn, Fe, Zn, Ag, Zr, Mo, Nb, Cu, Cr and Ti, and the conductive carbon is selected from at least one of graphene, carbon nanotubes, conductive carbon black and acetylene black;
the content of the conductive carbon in the sodium-ion battery positive electrode material is 1-10 wt%;
the specific surface area of the positive electrode material of the sodium-ion battery is 0.3-1.2 m2(ii)/g; and/or
The D50 particle size of the positive electrode material of the sodium ion battery is 5-30 nm.
Optionally, the specific surface area of the positive electrode material of the sodium-ion battery is 0.7-1.0 m2(ii)/g; and/or
The D50 particle size of the positive electrode material of the sodium-ion battery is 10-20 nm; and/or
The content of the conductive carbon in the positive electrode material of the sodium-ion battery is 3-5 wt%.
Preferably, the content of the conductive carbon in the positive electrode material of the sodium-ion battery is 4 wt%.
Preferably, the specific surface area of the positive electrode material of the sodium-ion battery is 0.9-1.0 m2/g。
Preferably, the particle size of the positive electrode material of the sodium-ion battery is 15-17 nm.
Alternatively, the NaxNiyM1-yO2@ 0.6-0.9 of x and 0.2-0.4 of y.
Preferably, the Na isxNiyM1-yO2@ conductive carbon, x is more than or equal to 0.8 and less than or equal to 0.85, and y is more than or equal to 0.3 and less than or equal to 0.35; more preferably, x is 0.67 and y is 0.33; and/or
M in the positive electrode material of the sodium-ion battery is selected from at least one of Mn, Fe, V, Cu, Cr and Ti; preferably, the M is selected from at least one of Mn, Fe and Cr; more preferably, M is Mn; and/or
The conductive carbon is graphene.
According to another aspect of the present application, there is provided a method for preparing the positive electrode material for sodium-ion battery, which comprises the following steps:
(1) mixing sodium salt, nickel salt, M salt, conductive carbon and a solvent to form mixed slurry;
(2) atomizing the mixed slurry and then directly calcining to obtain the positive electrode material of the sodium-ion battery;
wherein the M salt is at least one selected from the group consisting of Mn salt, Fe salt, V salt, Zn salt, Ag salt, Zr salt, Mo salt, Nb salt, Cu salt, Cr salt and Ti salt; the conductive carbon is selected from at least one of graphene, carbon nanotubes, conductive carbon black and acetylene black.
Optionally, the molar ratio of sodium atoms, nickel atoms and M atoms in the mixed slurry is 0.5-1: 0.1-0.5: 0.5 to 0.9;
preferably, the molar ratio of sodium atoms, nickel atoms and M atoms in the mixed slurry is 0.67:0.33: 0.67.
optionally, the sodium salt is selected from at least one of sodium carbonate, sodium nitrate, sodium acetate, and sodium hydroxide; preferably, the sodium salt is sodium acetate; and/or
The nickel salt is selected from divalent nickel salts; preferably, the divalent nickel salt is selected from at least one of nickel acetate, nickel acetate hydrate, nickel carbonate hydrate, nickel nitrate hydrate and nickel hydroxide; more preferably, the nickel salt is nickel acetate tetrahydrate; and/or
The M salt is selected from at least one of acetate, acetate hydrate, carbonate hydrate, chloride and hydroxide; preferably, the M salt is manganese acetate tetrahydrate.
The solvent in the mixed slurry is selected from at least one of water, ethanol and isopropanol.
Preferably, the solvent is ethanol.
The conductive carbon is graphene.
Optionally, in the step (1), adding the sodium salt, the nickel salt, the M salt and the conductive carbon into the solvent according to a certain proportion, and performing ball milling, ultrasonic dispersion and screening to obtain the mixed slurry;
preferably, a planetary ball mill is adopted for ball milling, and the mesh number of the screen is 100-800 meshes; more preferably, the mesh number of the screen is 300 meshes.
Optionally, the mixed slurry is ball milled using a planetary ball mill.
Optionally, in the step (2), a first inactive gas is used as a shielding gas, and the mixed slurry is atomized in a high-temperature reaction furnace;
atomizing the mixed slurry by an atomization system, wherein the atomization pressure of the atomization system is 1.0-20 MPa; preferably, the atomization pressure of the atomization system is 5-10 MPa; more preferably, the atomization pressure of the atomization system is 8 MPa; and/or
The temperature in the high-temperature reaction furnace is 100-300 ℃; preferably, the temperature in the high-temperature reaction furnace is 200 ℃.
The first inactive gas is selected from one of nitrogen, argon or helium; preferably, the first inert gas is nitrogen.
The atomization amount of the atomization system is 15-80 mL/min; preferably, the atomization amount of the atomization system is 30-50 mL/min; more preferably, the atomization amount of the atomization system is 40 mL/min.
Optionally, in the step (2), the mixed slurry is atomized and then calcined in a second inactive gas, the calcining temperature is 600-1000 ℃, and the calcining time is not less than 6 hours; preferably, the calcining temperature is 700-800 ℃, and the calcining time is 6-15 h; more preferably, the calcining temperature is 800 ℃ and the calcining time is 10 h.
The second inactive gas is selected from one of nitrogen, argon or helium; preferably, the second inert gas is nitrogen.
According to still another aspect of the present application, there is provided a sodium-ion battery, wherein the positive electrode material of the sodium-ion battery is selected from at least one of the positive electrode materials of the sodium-ion battery described above and the positive electrode material of the sodium-ion battery produced by the production method described in any one of the above.
Benefits of the present application include, but are not limited to:
1. the positive electrode material of the sodium ion battery is nano-sized, has the advantages of high dispersibility, large specific surface area and the like, is convenient for the rapid transfer of sodium ions and electrons in a material body phase, is beneficial to improving the cycle performance and rate capability of the material, and can improve the charge-discharge capacity, specific capacity, cycle stability and service life of the sodium ion battery; in addition, the positive electrode material does not contain cobalt, but has the energy density and the charge-discharge capacity equivalent to or even superior to those of a cobalt-containing battery, and has the advantages of good chemical stability, excellent safety performance and low price.
2. According to the sodium ion battery anode material, the graphene is added to serve as a carrier of transition metal oxide particles, crystal grain growth can be effectively controlled, crystal grains inside the material are arranged in order, the structural stability of the electrode material can be maintained, particle agglomeration can be prevented, contact resistance between the transition metal oxide particles is greatly reduced, the cycle performance and the rate performance of the material are greatly improved, in addition, the transition metal oxide particles can prevent stacking between graphene sheet layers, meanwhile, the excellent conductivity of the graphene accelerates the electron mobility of the anode material, and the conductivity of the anode material is effectively improved.
3. The preparation method of the sodium-ion battery cathode material is simple in process and low in price, and the prepared cathode material is controllable in size and easy to realize large-scale production.
4. According to the preparation method of the sodium ion battery cathode material, the conductive carbon, the sodium salt, the nickel salt and the M salt are added into the solvent together, and the process of dissolving the inorganic salt can promote the dispersion of the conductive carbon in the solvent at the same time, so that the conductive carbon is dispersed more uniformly, and the inorganic nano particles in the prepared cathode material are uniformly loaded on the surface of the conductive carbon; in addition, the conductive carbon is further dispersed more uniformly by a ball milling method, and the particle size uniformity of the conductive carbon in the anode material is ensured by the sieving net, so that the reversible capacity of the battery is effectively improved, and the cycle performance of the battery is improved.
5. According to the preparation method of the sodium ion battery cathode material, the particle size of the cathode material is regulated and controlled by controlling the atomization condition, the obtained cathode material is uniform in particle size, more storage active sites are provided for sodium ions, the first charge and discharge capacity and the first efficiency of the battery can be improved, and the scratch or strip breakage phenomenon in the subsequent coating and forming process can be prevented.
6. According to the preparation method of the sodium-ion battery cathode material, the structure of the cathode material is more stable through the calcination process, so that the material still has good cycle stability and long service life under the condition of high-rate charge and discharge, and the reversibility is excellent.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the application and together with the description serve to explain the application and not to limit the application. In the drawings:
fig. 1 is a schematic diagram of a first charge-discharge curve of a soft-package battery composed of a positive electrode material 1# and hard carbon according to an embodiment of the present application;
fig. 2 is a discharge capacity curve of a soft package battery composed of a positive electrode material 1# and hard carbon according to an embodiment of the present application at different current densities;
fig. 3 is a cycle performance curve of a pouch battery composed of a positive electrode material 1# to hard carbon according to an example of the present application.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Example 1 cathode Material 1#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O, 10g graphene and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a planetary ball milling tank containing 1L of ethanol, performing ball milling for 2 hours, performing ultrasonic treatment for 30min, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material No. 1.
Fig. 1 is a first charge-discharge curve (voltage range is 1.0-4.2V, current density is 0.1C) of a soft package battery composed of a positive electrode material 1# and hard carbon, and it can be seen from the figure that the specific charge capacity is 163mAh/g and the specific discharge capacity is 148 mAh/g.
Fig. 2 is a discharge capacity curve of positive electrode material # 1 versus soft-package battery composed of hard carbon under different current densities. It can be seen from the figure that: the average specific discharge capacities of the soft-package battery composed of the positive electrode material # 1 and the hard carbon at current densities of 0.1C, 1C, 2C, 3C, 4C, 10C and 0.1C were 148.0, 145.9, 138.7, 136.3, 130.2, 117.9 and 140.5mAh/g, respectively, and thus it can be seen that: the capacity retention rate of the anode material under different current densities is more than 99%; with the increase of the current density, polarization can be caused to cause the structural change of the material per se, so that the discharge capacity of the battery is obviously reduced, however, when the current density returns to 0.1C, the specific discharge capacity of the cathode material is 140.5mAh/g, which indicates that the reversibility of the cathode material is better.
Fig. 3 is a cycle performance curve (voltage range is 1.0-4.2V, current density is 1C) of the soft package battery composed of the positive electrode material 1# and hard carbon, and it can be seen from the figure that the specific capacity of the battery is kept better after 100 cycles, because the positive electrode material 1# is fully activated during the cycle process, and has stronger sodium storage capacity, thereby increasing the specific capacity.
Example 2 cathode Material 2#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O, 10g graphene and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a planetary ball milling tank containing 1L of ethanol, performing ball milling for 2 hours, performing ultrasonic treatment for 30min, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 700 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material No. 2.
Example 3 cathode Material 3#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O, 10g carbon nanotubes and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a planetary ball milling tank containing 1L of ethanol, performing ball milling for 2 hours, performing ultrasonic treatment for 30min, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (3) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material No. 3.
Example 4 cathode material 4#
(1) 77.9g of CH3COONa、74.6g(CH3COO)2Ni·4H2O, 10g graphene and 171.5g (CH)3COO)2Mn·4H2Respectively adding O (the molar ratio of Na, Ni and Mn is 0.95:0.3:0.7) into a planetary ball milling tank containing 1L of ethanol, performing ball milling for 2 hours, performing ultrasonic treatment for 30min, and then sieving by using a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (3) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material No. 4.
Example 5 cathode Material 5#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O, 10g graphene and 164.2g (CH)3COO)2Mn·4H2Adding O (the molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a planetary ball milling tank containing 1L of ethanol, performing ball milling for 2 hours, performing ultrasonic treatment for 30min, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (3) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomization amount is 30mL/min, and the atomization pressure is 5MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the cathode material No. 5.
Example 6 Positive electrode Material 6#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O, 10g graphene and 164.2g (CH)3COO)2Mn·4H2Adding O (molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a tank containing 1L ethanol, performing ultrasonic treatment for 30min, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material No. 6.
Comparative example 1 cathode material D1#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O and 164.2g (CH)3COO)2Mn·4H2Adding O (molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a planetary ball milling tank containing 1L of ethanol, ball milling for 2h, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material D1 #.
Comparative example 2 cathode material D2#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O and 164.2g (CH)3COO)2Mn·4H2Adding O (molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into a planetary ball milling tank containing 1L of ethanol, ball milling for 2h, and sieving with a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount is 100mL/min, the atomizing pressure is 25MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material D2 #.
Comparative example 3 cathode material D3#
(1) Adding 55g of CH3COONa、82.1g(CH3COO)2Ni·4H2O, 10g graphene and 164.2g (CH)3COO)2Mn·4H2Adding O (molar ratio of Na, Ni and Mn is 0.67:0.33:0.67) into planetary ball milling tank containing 1L ethanol, ball milling for 2 hr, ultrasonic treating for 30min, and sieving with 300 mesh sieve to obtain productUniformly mixing the slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 1200 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material D3 #.
Comparative example 4 cathode material D4#
(1) 86.1g of CH3COONa、49.8g(CH3COO)2Ni·4H2O, 10g graphene and 196.1g (CH)3COO)2Mn·4H2Respectively adding O (the molar ratio of Na to Ni to Mn is 1.05:0.2:0.8) into a planetary ball milling tank containing 1L of ethanol, performing ball milling for 2 hours, performing ultrasonic treatment for 30min, and then sieving by using a 300-mesh sieve to obtain uniform mixed slurry;
(2) and (2) atomizing the mixed slurry into small fog drops in a high-temperature reaction furnace by taking nitrogen as protective gas, wherein the temperature of the high-temperature reaction furnace is 200 ℃, the atomizing amount of an atomizing system is 40mL/min, the atomizing pressure is 8MPa, and then calcining the atomized small fog drops at 800 ℃ for 10 hours in the nitrogen protective atmosphere to obtain the anode material D4 #.
Examples of the experiments
The positive electrode materials obtained in examples 1 to 6 and comparative examples D1 to D4 were tested for tap density, specific surface area, particle size, specific charge-discharge capacity, energy density, and capacity retention rate after 100 cycles by the following methods, and the test results are shown in table 1.
Tap density: 25g of the anode material is taken, the tap density of the anode material is tested by a tap density instrument, and three groups of the anode material are tested in parallel to obtain an average value.
Specific surface area: the specific surface area of the anode material is tested by a BET specific surface area tester, and three groups are tested in parallel to obtain an average value.
Particle size: 0.1g of the anode material is weighed and placed in 100mL of absolute ethyl alcohol, magnetic stirring is carried out for 5min, ultrasonic dispersion is carried out for 3min, the particle size is measured by a laser particle sizer, and three groups are tested in parallel to obtain an average value.
Charge-discharge specific capacity and energy density: taking the positive electrode material: PVDF: SP 88: 6: and 6, taking hard carbon as a cathode, taking sodium hexafluorophosphate as an electrolyte, assembling the soft package battery, and testing the charge-discharge specific capacity and the energy density of the soft package battery under the conditions that the voltage range is 1.0-4.2V and the current density is 0.1C.
Capacity retention after 100 weeks cycling: taking the positive electrode material: PVDF: SP 88: 6: and 6, assembling the soft package battery by taking hard carbon as a cathode and sodium hexafluorophosphate as electrolyte, and performing a discharge test of 100 cycles at a voltage range of 1.0-4.2V and a current density of 1C to obtain a capacity retention curve after 100 cycles.
TABLE 1
The experimental data show that the tap densities of the cathode material prepared by the invention are all more than 1.35g/cm3The volume energy density of the battery is improved; the specific surface areas are all larger than 0.7m2The volume expansion of the battery in the charging and discharging process is reduced, and the cycling stability of the battery is improved; the soft package battery assembled by the positive electrode material has the first charge specific capacity of more than 155mAh/g and the discharge specific capacity of more than 130mAh/g, which shows that the charge-discharge capacity is excellent, the capacity retention rate is more than 90 percent after 100-week circulation, and the energy density is higher than 135 Wh/Kg.
The above description is only an example of the present application, and the protection scope of the present application is not limited by these specific examples, but is defined by the claims of the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the technical idea and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. The positive electrode material of the sodium-ion battery is characterized in that the chemical composition of the positive electrode material of the sodium-ion battery is NaxNiyM1-yO2@ electric conductionCarbon;
wherein x is more than or equal to 0.5 and less than or equal to 1, y is more than or equal to 0.1 and less than or equal to 0.5, M is selected from at least one of Mn, Fe, Zn, Ag, Zr, Mo, Nb, Cu, Cr and Ti, and the conductive carbon is selected from at least one of graphene, carbon nanotubes, conductive carbon black and acetylene black;
the content of the conductive carbon in the sodium-ion battery positive electrode material is 1-10 wt%;
the specific surface area of the positive electrode material of the sodium-ion battery is 0.3-1.2 m2(ii)/g; and/or
The D50 particle size of the positive electrode material of the sodium ion battery is 5-30 nm.
2. The positive electrode material for sodium-ion batteries according to claim 1, wherein the specific surface area of the positive electrode material for sodium-ion batteries is 0.7-1.0 m2(ii)/g; and/or
The D50 particle size of the positive electrode material of the sodium-ion battery is 10-20 nm; and/or
The content of the conductive carbon in the sodium-ion battery positive electrode material is 3-5 wt%;
preferably, the content of the conductive carbon in the positive electrode material of the sodium-ion battery is 4 wt%.
3. The positive electrode material for sodium-ion batteries according to claim 1, wherein said Na isxNiyM1-yO2@ 0.6-0.9 x, 0.2-0.4 y; more preferably, x is 0.67 and y is 0.33; and/or
M in the positive electrode material of the sodium-ion battery is selected from at least one of Mn, Fe, V, Cu, Cr and Ti; preferably, the M is selected from at least one of Mn, Fe and Cr; more preferably, M is Mn; and/or
The conductive carbon is graphene.
4. A method for preparing a positive electrode material for a sodium-ion battery according to any one of claims 1 to 3, characterized in that it comprises the steps of:
(1) mixing sodium salt, nickel salt, M salt, conductive carbon and a solvent to form mixed slurry;
(2) atomizing the mixed slurry and then directly calcining to obtain the positive electrode material of the sodium-ion battery;
wherein the M salt is at least one selected from the group consisting of Mn salt, Fe salt, V salt, Zn salt, Ag salt, Zr salt, Mo salt, Nb salt, Cu salt, Cr salt and Ti salt; the conductive carbon is selected from at least one of graphene, carbon nanotubes, conductive carbon black and acetylene black.
5. The method for preparing the positive electrode material of the sodium-ion battery according to claim 4, wherein the molar ratio of the sodium atoms to the nickel atoms to the M atoms in the mixed slurry is 0.5-1: 0.1-0.5: 0.5 to 0.9;
preferably, the molar ratio of sodium atoms, nickel atoms and M atoms in the mixed slurry is 0.67:0.33: 0.67.
6. the method for producing a positive electrode material for a sodium-ion battery according to claim 4, wherein the sodium salt is at least one selected from the group consisting of sodium carbonate, sodium nitrate, sodium acetate, and sodium hydroxide; preferably, the sodium salt is sodium acetate; and/or
The nickel salt is selected from divalent nickel salts; preferably, the divalent nickel salt is selected from at least one of nickel acetate, nickel acetate hydrate, nickel carbonate hydrate, nickel nitrate hydrate and nickel hydroxide; more preferably, the nickel salt is nickel acetate tetrahydrate; and/or
The M salt is selected from at least one of acetate, acetate hydrate, carbonate hydrate, chloride and hydroxide; preferably, the M salt is manganese acetate tetrahydrate.
7. The method for preparing the sodium-ion battery cathode material according to any one of claims 4 to 6, wherein the sodium salt, the nickel salt, the M salt and the conductive carbon are added into the solvent according to a certain proportion in the step (1), and the mixture is subjected to ball milling, ultrasonic dispersion and sieving to obtain the mixed slurry;
preferably, the mesh number of the screen is 100-800 meshes; more preferably, the mesh number of the screen is 300 meshes.
8. The method for preparing a positive electrode material for a sodium-ion battery according to any one of claims 4 to 6, wherein the mixed slurry is atomized in the high-temperature reaction furnace using the first inactive gas as a shielding gas in the step (2);
atomizing the mixed slurry by an atomization system, wherein the atomization pressure of the atomization system is 1.0-20 MPa; preferably, the atomization pressure of the atomization system is 5-10 MPa; more preferably, the atomization pressure of the atomization system is 8 MPa; and/or
The temperature in the high-temperature reaction furnace is 100-300 ℃; preferably, the temperature in the high-temperature reaction furnace is 200 ℃.
9. The method for preparing the sodium-ion battery cathode material according to any one of claims 4 to 6, wherein in the step (2), the mixed slurry is atomized and then calcined in a second inactive gas, wherein the calcination temperature is 600-1000 ℃, and the calcination time is not less than 6 h;
preferably, the calcining temperature is 800 ℃, and the calcining time is 10 h.
10. A sodium-ion battery, characterized in that the positive electrode material of the sodium-ion battery is selected from at least one of the positive electrode materials of the sodium-ion battery according to any one of claims 1 to 3 and the positive electrode material of the sodium-ion battery prepared by the preparation method according to any one of claims 4 to 9.
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| CN113666424A (en) * | 2021-09-29 | 2021-11-19 | 南通金通储能动力新材料有限公司 | Precursor of sodium ion battery anode material and preparation method thereof |
| CN114005987A (en) * | 2021-10-26 | 2022-02-01 | 山东玉皇新能源科技有限公司 | Sodium ion battery positive electrode material additive and sodium ion battery positive electrode material |
| CN114597327A (en) * | 2022-03-25 | 2022-06-07 | 浙江大学 | (FeCuZn) F3/rGO composite porous nano material and lithium fluorine battery |
| WO2024022431A1 (en) * | 2022-07-29 | 2024-02-01 | 湖北万润新能源科技股份有限公司 | Sodium-ion battery positive electrode material, and preparation method therefor and use thereof |
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| CN115557546B (en) * | 2022-12-06 | 2023-03-21 | 湖州超钠新能源科技有限公司 | Sodium ion positive electrode material and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113666424A (en) * | 2021-09-29 | 2021-11-19 | 南通金通储能动力新材料有限公司 | Precursor of sodium ion battery anode material and preparation method thereof |
| CN113666424B (en) * | 2021-09-29 | 2023-07-14 | 南通金通储能动力新材料有限公司 | Precursor of sodium ion battery anode material and preparation method thereof |
| CN114005987A (en) * | 2021-10-26 | 2022-02-01 | 山东玉皇新能源科技有限公司 | Sodium ion battery positive electrode material additive and sodium ion battery positive electrode material |
| CN114005987B (en) * | 2021-10-26 | 2024-03-22 | 山东玉皇新能源科技有限公司 | Additive for positive electrode material of sodium ion battery and positive electrode material of sodium ion battery |
| CN114597327A (en) * | 2022-03-25 | 2022-06-07 | 浙江大学 | (FeCuZn) F3/rGO composite porous nano material and lithium fluorine battery |
| CN114597327B (en) * | 2022-03-25 | 2024-04-09 | 浙江大学 | (FeCuZn) F 3 rGO composite porous nano material and lithium-fluorine battery |
| WO2024022431A1 (en) * | 2022-07-29 | 2024-02-01 | 湖北万润新能源科技股份有限公司 | Sodium-ion battery positive electrode material, and preparation method therefor and use thereof |
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