CN116161705A - High-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ Preparation method of sodium ion battery anode material - Google Patents

High-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ Preparation method of sodium ion battery anode material Download PDF

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CN116161705A
CN116161705A CN202310122017.3A CN202310122017A CN116161705A CN 116161705 A CN116161705 A CN 116161705A CN 202310122017 A CN202310122017 A CN 202310122017A CN 116161705 A CN116161705 A CN 116161705A
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sintering
raw materials
temperature
partial pressure
ion battery
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刘国强
苏畅
闻雷
吴敏杰
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Kingpower Materials Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0072—Mixed oxides or hydroxides containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
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    • C01—INORGANIC CHEMISTRY
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to a high-performance manganese-iron-based Na 0.67 TM x Mn 0.9‑x Fe 0.1 O 2‑δ A preparation method of a sodium ion battery anode material belongs to the technical field of energy storage materials. By adopting a method of combining oxygen partial pressure and doping transition metal elements in the sintering heat preservation process, oxygen vacancies with proper content are introduced into the material, and meanwhile, transition metal elements (TM) are doped to modify the lattice structure of the material, so that the lattice change of the material in the charge-discharge process is reduced, and the electrochemical performance of the material is more stable. The invention is characterized in that the material is doped with the same excessive metal element by regulating the type and the content of the doped transition metal and changing the oxygen partial pressure in the sintering process of the materialWhen an appropriate amount of oxygen vacancies are introduced (i.e. synthesizing Na 0.67 TM x Mn 0.9‑x Fe 0.1 O 2‑δ ) The lattice change of the material in the charge-discharge process is reduced, so that the electrochemical performance of the material is more stable.

Description

High-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ Preparation method of sodium ion battery anode material
Technical field:
the invention relates to a high-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ A preparation method of a sodium ion battery anode material belongs to the technical field of energy storage materials.
The background technology is as follows:
with the development of renewable energy sources, the demand of energy storage systems in human society is increasing. Sodium element has abundant reserves in crust, wide distribution and low cost, so that sodium ion battery research has attracted great attention in recent years. The sodium ion battery is used as a novel energy storage material, and can be applied to the fields of low-speed electric vehicles, communication base stations, household energy storage, power grid energy storage and the like which have relatively low energy density requirements and are sensitive to cost in the future.
The positive electrode material is an important part affecting the performance and cost of the sodium ion battery. In the current research and development of the positive electrode material of the sodium ion battery, the Mn and Fe-based layered oxide material has the advantages of rich raw material resources, low cost, environmental friendliness and the like, and has good application potential. However, na 0.67 Mn 0.9 Fe 0.1 O 2 During the charge and discharge process of the material, MO is used 6 The M-O (m=mn, fe) bond length changes in the octahedral structure, i.e. the octahedron is deformed, resulting in a change in lattice constant, na + Ion layer spacing changes and also initiates Fe 4+ Migration to Na layer locations, etc., ultimately leads to performance degradation such as decay of specific capacity, voltage, cycling performance, and rate performance. The research reduces lattice distortion, improves the electrochemical performance of the material, and has good scientific significance and application value.
Disclosure of Invention
For Na 0.67 Mn 0.9 Fe 0.1 O 2 The invention provides a high-performance manganese-iron-based Na, which solves the problem of capacity attenuation caused by lattice change of a positive electrode material in the charge-discharge process 0.67 TM x Mn 0.9-x Fe0.1O 2-δ Sodium ionThe preparation method of the sub-battery anode material combines doping elements with the introduction of oxygen vacancies, thereby not only improving the capacity retention capacity of the battery, but also effectively improving the multiplying power performance of the battery.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
high-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ The preparation method of the sodium ion battery anode material comprises the following steps:
the first step: weighing and mixing
(1) According to Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ The ratio of the stoichiometric number of the metal cations in the raw materials is measured to obtain Na, mn, fe, TM raw materials with corresponding mass; wherein, x ranges from 0.05 to 0.20, delta ranges from 0.03 to 0.21, and TM is one of transition metal elements Cu, ni and Ti;
(2) Ball-milling and uniformly mixing the weighed raw materials, and drying in a drying oven after ball milling is completed;
and a second step of: sample preparation and sintering
(1) Pressing the uniformly mixed raw materials into blocks;
(2) Placing the block raw materials into a tube furnace, raising the temperature to a sintering temperature at a constant temperature raising rate under an air atmosphere, then introducing oxygen partial pressure gas, sintering under the air atmosphere, and preserving the temperature for a period of time;
(3) And after the sintering heat preservation is completed, cooling to room temperature.
In the first step (1), na is NaNO as a raw material 3 、Na 2 CO 3 One or more than two of NaOH.
In the first step (1), mn raw materials are MnO and Mn 2 O 3 、MnO 2 One or two or more of them.
In the first step (1), the Fe raw material is FeO and Fe 2 O 3 、Fe 3 O 4 One or two or more of them.
In the second step (2), the constant temperature rising rate is 3-10 ℃/min.
In the second step (2), the sintering temperature is a certain temperature in the range of 750-1150 ℃.
In the second step (2), the heat preservation time is 8-16 h.
In the second step (2), the partial pressure of oxygen is O 2 Mixed with Ar and has an oxygen partial pressure of a certain value within a range of 0.15 to 0.30 atm.
In the second step (3), the cooling rate for cooling to room temperature is 3-20 ℃/min.
The design idea of the invention is as follows:
the invention provides a method for improving the electrochemical performance of a positive electrode material of a sodium ion battery by controlling the combination of oxygen partial pressure and doping transition metal elements in the sintering heat preservation process, which comprises the following steps of 0.67 Mn 0.9 Fe 0.1 O 2 The sodium ion battery anode material is introduced with a certain content of oxygen vacancies and doped with a certain content of transition metals, and the high-performance manganese-iron-based Na is successfully synthesized 0.67 TM x Mn 0.9-x Fe0.1O 2-δ A positive electrode material of a sodium ion battery. At Na (Na) 0.67 Mn 0.9 Fe 0.1 O 2 Introducing oxygen vacancies in an appropriate amount to cause MO 6 The M-O (M=Mn, fe) bond length in the octahedral structure is changed, so that the ginger-Taylor distortion caused by charge compensation in the charging and discharging processes of Mn and Fe elements is reduced, the structural stability of the material in the charging and discharging processes is enhanced, and meanwhile, the lattice spacing of the layered oxide material can be improved by using Transition Metal (TM) for element doping, and Na ions are removed and embedded in the charging and discharging processes. The comprehensive method improves the discharge specific capacity, the cycle retention rate and the multiplying power performance of the raw materials.
The invention has the advantages and beneficial effects that:
1. to reduce Na 0.67 Mn 0.9 Fe 0.1 O 2 The invention provides a method for preparing a material with a crystal lattice change and solving the problem of poor cycle performance 0.67 Mn 0.9 Fe 0.1 O 2 The material is modified completely by means of combining partial pressure of oxygen and doped transition metal element during sintering and maintaining, and has proper oxygen vacancy content introducedThe transition metal element (TM) is doped to modify the lattice structure of the material, so that the Na ion layer spacing in the layered structure is increased, the lattice change of the material in the charge-discharge process is reduced, and the electrochemical performance of the material is more stable.
2. The invention relates to a high-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe0.1O 2-δ The preparation method of the sodium ion battery anode material reduces the lattice change degree of the material in charge-discharge cycle and improves the comprehensive electrochemical performance of the material. The material is used as a positive electrode material of a sodium ion battery for charge and discharge test, and the charge and discharge test voltage range is as follows: 2.0-4.0V, current density of 100mA/g and test temperature of 25 ℃. Test results show that Na prepared by the preparation method related in the invention 0.67 Cu 0.05 Mn 0.85 Fe 0.1 O 1.91 The initial discharge capacity of the positive electrode material is 173.2mAh/g, the capacity retention rate after 100 circles is 88.1%, and the capacity can reach 89mAh/g when the test current density is 2000 mA/g. The material prepared by the process has good comprehensive performance, has wide application prospect and is convenient for practical production and application.
Drawings
FIG. 1 is a graph showing the cycle capacity at 25℃of the sample provided in example 1 of the present invention. In the figure, the abscissa Cycle number represents the number of cycles, and the ordinate Capacity represents the Capacity (mAh/g).
FIG. 2 is a graph of the cycling capacity at 25℃of the sample provided in example 2 of the present invention. In the figure, the abscissa Cycle number represents the number of cycles, and the ordinate Capacity represents the Capacity (mAh/g).
FIG. 3 is a graph showing the cycle capacity at 25℃of the sample provided in example 3 of the present invention. In the figure, the abscissa Cycle number represents the number of cycles, and the ordinate Capacity represents the Capacity (mAh/g).
Detailed Description
In the concrete implementation process, in order to reduce Na 0.67 Mn 0.9 Fe 0.1 O 2 The invention provides a high-performance manganese-iron-based Na, which has the advantages of changing the crystal lattice of the material and solving the problem of poor cycle performance 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ The preparation method of the sodium ion battery anode material is to change the oxygen partial pressure in the sintering heat preservation process to increase Na 0.67 Mn 0.9 Fe 0.1 O 2 The oxygen vacancy content in the material and the doping transition metal element (TM) modify the lattice structure of the material, so that the purposes of reducing the lattice degree in the charge-discharge process and improving the electrochemical performance of the material are finally achieved.
The experimental methods described in the following examples, unless otherwise specified, are all conventional: the reagents and materials, unless otherwise specified, are commercially available.
Example 1
In this embodiment, a high performance Na 0.67 Cu 0.05 Mn 0.85 Fe 0.1 O 1.91 The preparation method of the sodium ion battery electrode material comprises the following steps:
the first step: weighing and mixing
(1) According to Na 0.67 Cu 0.05 Mn 0.85 Fe 0.1 O 1.91 The stoichiometric ratio of the metal cations in the mixture, and weighing Na with corresponding mass 2 CO 3 、MnO 2 FeO and metallic Cu raw materials;
(2) Ball-milling and uniformly mixing the weighed raw materials, and drying in a drying oven after ball milling is completed;
and a second step of: sample preparation and sintering
(1) Pressing the uniformly mixed raw materials into blocks;
(2) The bulk raw material is placed in a tube furnace, heated to 900 ℃ at a heating rate of 8 ℃/min under the air atmosphere, and then Ar/O with oxygen partial pressure of 0.18atm is introduced 2 The mixture (1 atm) was kept at this atmosphere for 10 hours;
(3) And (5) completing sintering heat preservation, and cooling to room temperature at a cooling speed of 15 ℃/min.
As shown in FIG. 1, for synthetic Na 0.67 Cu 0.05 Mn 0.85 Fe 0.1 O 1.91 The positive electrode material is subjected to half-cell charge and discharge test under the current density of 100mA/g, and the initial discharge specific capacity can be seen from the cyclic capacity diagram of the sample at 25 DEG C173.2mAh g -1 The capacity retention after 100 charge and discharge cycles was 88.1%.
Example 2
In this embodiment, a high performance Na 0.67 Ti 0.2 Mn 0.7 Fe 0.1 O 1.97 The preparation method of the sodium ion battery electrode material comprises the following steps:
the first step: weighing and mixing
(1) According to Na 0.67 Ti 0.2 Mn 0.7 Fe 0.1 O 1.91 The ratio of the stoichiometric numbers of the metal cations in the water-soluble polymer is measured out to obtain NaOH, mnO, fe of corresponding mass 2 O 3 And a metallic Ti feedstock;
(2) Ball-milling and uniformly mixing the weighed raw materials, and drying in a drying oven after ball milling is completed;
and a second step of: sample preparation and sintering
(1) Pressing the uniformly mixed raw materials into blocks;
(2) The bulk raw material is placed in a tube furnace, heated to 750 ℃ at a heating rate of 3 ℃/min under the air atmosphere, and then Ar/O with the oxygen partial pressure of 0.30atm is introduced 2 The mixture (1 atm) was kept at this atmosphere for 16 hours;
(3) And (3) completing sintering heat preservation, and cooling to room temperature at a cooling speed of 20 ℃/min.
As shown in FIG. 2, for synthetic Na 0.67 Ti 0.2 Mn 0.7 Fe 0.1 O 1.91 The positive electrode material is subjected to half-cell charge-discharge test under the current density of 100mA/g, and the initial discharge specific capacity is 143.2mAh g as can be seen from the cyclic capacity diagram of the sample at 25 DEG C -1 The capacity retention after 100 charge and discharge cycles was 70.5%.
Example 3
In this embodiment, a high performance Na 0.67 Ni 0.15 Mn 0.75 Fe 0.1 O 1.79 The preparation method of the sodium ion battery electrode material comprises the following steps:
the first step: weighing and mixing
(1) According to Na 0.67 Ni 0.15 Mn 0.75 Fe 0.1 O 1.79 The stoichiometric ratio of the metal cations in the water-soluble magnesium alloy is measured to obtain NaOH and Mn with corresponding mass 2 O 3 、Fe 3 O 4 And a metallic Ni feedstock;
(2) Ball-milling and uniformly mixing the weighed raw materials, and drying in a drying oven after ball milling is completed;
and a second step of: sample preparation and sintering
(1) Pressing the uniformly mixed raw materials into blocks;
(2) The bulk raw material is placed in a tube furnace, heated to 1150 ℃ at a heating rate of 8 ℃/min under the air atmosphere, and then Ar/O with oxygen partial pressure of 0.15atm is introduced 2 The mixture (1 atm) was kept at this atmosphere for 8 hours;
(3) And (3) sintering, heat preservation and cooling to room temperature at a cooling speed of 3 ℃/min.
As shown in FIG. 3, for synthetic Na 0.67 Ni 0.15 Mn 0.75 Fe 0.1 O 1.79 The positive electrode material is subjected to half-cell charge and discharge test under the current density of 100mA/g, and the initial discharge specific capacity is 171.2mAh g as can be seen from the cyclic capacity diagram of the sample at 25 DEG C -1 The capacity retention after 100 charge and discharge cycles was 68.1%.
The invention changes the oxygen partial pressure to Na in the material sintering process by regulating and controlling the type and the content of the doped transition metal 0.67 Mn 0.9 Fe 0.1 O 2 The material is modified, and is used as a positive electrode material of the sodium ion battery for charge and discharge test, and the charge and discharge test voltage range is as follows: 2.0-4.0V, current density of 100mA/g and test temperature of 25 ℃. Test results show that the capacity retention rates of the positive electrode materials prepared in different sintering atmospheres after 100 circles of circulation are respectively as follows: 88.1%, 70.5%, 68.1%.
The implementation result shows that the invention introduces proper content of oxygen vacancies (namely synthesizing Na) while doping excessive metal elements in the material by regulating the type and the content of the doped transition metal and changing the oxygen partial pressure in the sintering process of the material 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ ) And reduceThe lattice change of the material in the charge and discharge process ensures that the electrochemical performance of the material is more stable. In addition, the electrode material can be prepared by a solid phase method, the process is simple and feasible, the raw materials are cheap and easy to obtain, and the mass industrialized production is easy to realize.

Claims (9)

1. High-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ The preparation method of the sodium ion battery anode material is characterized by comprising the following steps:
the first step: weighing and mixing
(1) According to Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ The ratio of the stoichiometric number of the metal cations in the raw materials is measured to obtain Na, mn, fe, TM raw materials with corresponding mass; wherein, x ranges from 0.05 to 0.20, delta ranges from 0.03 to 0.21, and TM is one of transition metal elements Cu, ni and Ti;
(2) Ball-milling and uniformly mixing the weighed raw materials, and drying in a drying oven after ball milling is completed;
and a second step of: sample preparation and sintering
(1) Pressing the uniformly mixed raw materials into blocks;
(2) Placing the block raw materials into a tube furnace, raising the temperature to a sintering temperature at a constant temperature raising rate under an air atmosphere, then introducing oxygen partial pressure gas, sintering under the air atmosphere, and preserving the temperature for a period of time;
(3) And after the sintering heat preservation is completed, cooling to room temperature.
2. The method of claim 1, wherein in step (1), the Na source material is NaNO 3 、Na 2 CO 3 One or more than two of NaOH.
3. The method according to claim 1, wherein in the first step (1), the Mn raw material is MnO, mn 2 O 3 、MnO 2 One or two or more of them.
4. As claimed inThe method according to claim 1, wherein in the first step (1), the Fe raw material is FeO or Fe 2 O 3 、Fe 3 O 4 One or two or more of them.
5. The method of claim 1, wherein in step (2) the constant temperature rise rate is 3 to 10 ℃/min.
6. The method according to claim 1, wherein in the second step (2), the sintering temperature is a temperature in the range of 750 to 1150 ℃.
7. The method according to claim 1, wherein in the second step (2), the holding time is 8 to 16 hours.
8. The process of claim 1, wherein in step (2), the oxygen partial pressure gas is O 2 Mixed with Ar and has an oxygen partial pressure of a certain value within a range of 0.15 to 0.30 atm.
9. The method according to claim 1, wherein in the second step (3), the cooling rate to room temperature is 3 to 20 ℃/min.
CN202310122017.3A 2023-02-15 2023-02-15 High-performance manganese-iron-based Na 0.67 TM x Mn 0.9-x Fe 0.1 O 2-δ Preparation method of sodium ion battery anode material Pending CN116161705A (en)

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