CN115411236A - Nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, preparation method and application - Google Patents
Nickel-iron-manganese-based material with aluminum phosphate/sodium phosphate modified surface, preparation method and application Download PDFInfo
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- 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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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a nickel-iron-manganese-based material with an aluminum phosphate/sodium phosphate modified surface, a preparation method and application thereof. The material is a layered oxide material, and the space group is
In the material, the aluminum phosphate formed in situ is distributed on the surface of the NaNiFeMn material, or is distributed on the surface of the NaNiFeMn material and is dispersed in the material body phase of the NaNiFeMn material; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material; the aluminum phosphate/phosphoric acidThe chemical general formula of the nickel-iron-manganese-based material on the sodium modified surface is as follows: alPO 4 @Na a [Ni b Fe c Mn d Me e ]O 2+β (ii) a Wherein the valence of Ni is +2, the valence of Fe is +3, the valence of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence is alpha; +2 is not less than alpha and not more than +4; a. b, c, d, e and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a nickel-iron-manganese-based material with an aluminum phosphate/sodium phosphate modified surface, a preparation method and application thereof.
Background
Since the industrial revolution, human society has entered a rapidly growing era, behind which there is a great consumption of traditional energy and environmental pollution. The consumption of fossil fuels is therefore subject to strict controls and new energy sources are sought. Nuclear power has been considered as a solution for future energy sources, but many countries have a tendency to restrict the use of nuclear power due to the safety problem that this technology has been difficult to solve completely. The energy viable approach in the future is to develop renewable energy sources such as hydraulic resources, wind energy and solar energy, with the advantage of no pollution and safety issues. However, one obvious disadvantage of developing these energy sources is that they are limited by geographical location or time, and they preferably need to be as close as possible to the electric energy consumption territory. Besides, one significant disadvantage of wind energy and solar energy is the discontinuity of power generation, i.e. the fluctuation of generated power is large, and constant power output cannot be achieved for a long time. The fluctuation period of the generated power of wind power generation varies from hours, days to weeks, while that of solar power generation is minutes or hours. Furthermore, solar cells can only produce near-nominal (peak current) electrical energy at noon of solar irradiation, however noon is not the most concentrated period of power consumption in a day. It is very inconvenient from the point of view of the power grid, which will not be able to be directly incorporated into the power grid. Electric power is the most convenient form of energy to reach, and the stable supply of the electric power determines the stable and orderly development of society. By the end of 2020, the accumulated installed scale of the energy storage projects already put into operation in China is 35.6GW, which is increased by 9.8% on year-on-year basis; the pumped storage accumulation installation accounts for the largest ratio of 89.30 percent, and then is electrochemical energy storage, and the accumulation installation scale is 3.28GW, which accounts for 9.2 percent; for large-scale energy storage, battery parameters that need to be considered include: price, lifetime and power density. It is necessary to use raw materials which are widely available (low cost). Under the background, in recent years, sodium ion batteries are paid more and more attention by researchers, and the world sodium resource is extremely sufficient, so that the application potential of the sodium ion batteries in the field of large-scale energy storage is very huge.
The main advantages of sodium ion batteries over lithium ion batteries are their low cost, mainly from two points: the abundance of sodium element in crust is much higher than that of lithium element, and the sodium element is distributed in all corners of the earth, and is not like lithium resource which is mainly distributed in south America and Australia; in addition, the current collector of the negative electrode in the sodium ion battery can use the metal aluminum with lower cost, and lithium reacts with aluminum to form an alloy and is irreversible. Therefore, the negative electrode of the lithium ion battery can only select copper foil with higher cost as a current collector. Besides low cost, another advantage of the sodium ion battery is that rapid industrialization can be realized by using a relatively mature production line of the lithium ion battery, which is more obvious than other emerging energy storage technologies, because most of the problems of the sodium ion battery can be solved in the lithium ion battery.
Compared with lithium of a lithium ion battery, the relative atomic mass and radius of sodium are larger, and the standard of sodium is higher than that of lithium in terms of hydrogen potential, so that theoretically, the energy density of the sodium ion battery is lower than that of the lithium ion battery, and according to the current production and manufacturing level of the sodium ion battery, the energy density is about half of that of the lithium ion battery. However, the energy density of the sodium ion battery is far higher than that of the lead-acid battery, and is about three times that of the lead-acid battery. The transition metal oxide with a layered structure is an embedded compound which is researched earlier, and has the characteristics of higher energy density and easiness in preparation. The general formula of the structure is Na x MO 2 (M represents one speciesOr a plurality of transition metal elements). Usually each transition metal element combines with six surrounding oxygens to form MO 6 Octahedron connected by common edges, sodium ion between transition metal layers to form MO 2 The layers and the Na layer are arranged alternately. The nickel-iron-manganese-based layered oxide material has low cost, and the price of the contained elements of sodium, nickel, iron and manganese is far lower than that of cobalt, vanadium and the like, but at present, the material has poor cycle stability, and further development of the material is limited.
Disclosure of Invention
The invention provides a nickel-iron-manganese-based material with an aluminum phosphate/sodium phosphate modified surface, a preparation method and application thereof. The nickel-iron-manganese-based layered oxide material is simple to prepare, and the contained elements of sodium, nickel, iron and manganese are nontoxic and safe elements. After the surface of the aluminum phosphate/sodium phosphate is modified, the side reaction of the electrode material and the electrolyte can be effectively inhibited, and the circulation stability is improved. In a half-cell test, the capacity retention rate of the nickel-iron-manganese-based oxide material improved by the method can be improved by about 20% before improvement, and the rate capability is good, so that the method has great practical value. The sodium ion secondary battery based on the nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power sources or communication base stations.
In a first aspect, the invention discloses an aluminum phosphate/sodium phosphate modified nickel-iron-manganese-based material, which is a layered oxide material with a space group of
In the material, the aluminum phosphate formed in situ is distributed on the surface of the NaNiFeMn material, or is distributed on the surface of the NaNiFeMn material and is dispersed in the material body phase of the NaNiFeMn material; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material;
the chemical general formula of the nickel-iron-manganese-based material on the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4 @Na a [Ni b Fe c Mn d Me e ]O 2+β ；
Wherein the valence of Ni is +2, the valence of Fe is +3, the valence of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; α is more than or equal to +2 and less than or equal to +4; a. b, c, d, e and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
preferably, the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is used as a positive electrode active material of a sodium ion secondary battery, when the nickel ion is charged for the first week, the nickel ion loses electrons, the valence state is changed from +2 valence to +3 valence, and meanwhile, the iron ion loses electrons, and the valence state is changed from +3 valence to +4 valence; during the first cycle of discharge, the nickel ions with higher valence state get electrons back to +2 valence state, and the iron ions get electrons back to +3 valence state.
Preferably, the aluminum phosphate/sodium phosphate surface-modified by the nickel-iron-manganese-based material does not participate in the redox reaction.
In a second aspect, the embodiment of the invention provides a preparation method of an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material, which comprises the following steps:
dissolving nitrates or sulfates of Ni, fe, mn and Me in water or absolute ethyl alcohol according to a stoichiometric ratio to form a precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
dripping the precursor solution into ammonia water solution with certain concentration and pH value by using a peristaltic pump to generate precipitate [ Ni ] b Fe c Mn d Me e ]O 2+β A precursor; wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, a, b, c, d, e and beta are respectively the mole percentage occupied by the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
is prepared from [ Ni b Fe c Mn d Me e ]O 2+β Precursor, 100-108 wt% of NaOH and/or Na with required stoichiometric amount 2 CO 3 0.01mol% to 5mol% of AlNO 3 0.01mol% -5 mol% of NH 4 H 2 PO 4 And/or (NH) 4 ) 2 HPO 4 Adding into water or anhydrous ethanol, heating and stirring until drying, and drying to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a third aspect, the embodiment of the invention provides a preparation method of an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material, which comprises the following steps:
sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium and NiO and Fe with the stoichiometric quantity of the required 2 O 3 And/or Fe 3 O 4 、Mn 2 O 3 And/or MnO 2 、MeO α/2 Mixing the raw materials into a precursor according to a certain proportion; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
adding absolute ethyl alcohol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder; mixing the precursor powder with AlNO in required stoichiometric amount 3 ,NH 4 H 2 PO 4 And/or (NH) 4 ) 2 HPO 4 Dispersing in deionized water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain coated precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a fourth aspect, the embodiment of the invention provides a preparation method of an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material, which comprises the following steps:
dissolving one or more of sodium acetate, sodium nitrate, sodium carbonate and sodium sulfate with the stoichiometric amount of 100-108 wt% of the required sodium and nitrate or sulfate containing Ni, fe, mn and Me in water or absolute ethyl alcohol according to the stoichiometric ratio to form precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
placing the precursor gel in a crucible, and presintering for 2 hours at 200-500 ℃ in air atmosphere to obtain a precursor;
mixing the precursor with AlNO in required stoichiometric amount 3 ，NH 4 H 2 PO 4 And/or (NH) 4 ) 2 HPO 4 Dispersing in water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
and then carrying out heat treatment at 600-1000 ℃ for 2-24 hours, and grinding the heat-treated powder to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a fifth aspect, the embodiment of the invention provides a preparation method of an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material, which comprises the following steps:
sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium and NiO and Fe with the stoichiometric quantity of the required 2 O 3 And/or Fe 3 O 4 、Mn 2 O 3 And/or MnO 2 、MeO α/2 Mixing the raw materials into a precursor according to a certain proportion; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
mixing the precursor powder with AlNO in required stoichiometric amount 3 ,(NH 4 ) 2 HPO 4 Dispersing in absolute ethyl alcohol, heating, stirring and evaporating to dryness;
placing the product obtained after evaporation to dryness in a muffle furnace, and carrying out heat treatment for 2-24 hours in an air atmosphere at 600-1000 ℃;
and grinding the product after the heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
In a sixth aspect, an embodiment of the present invention provides a positive electrode plate of a sodium ion secondary battery, where the positive electrode plate includes:
the aluminum phosphate/sodium phosphate modified nickel-iron-manganese-based material comprises a current collector, a conductive additive and a binder coated on the current collector, and the aluminum phosphate/sodium phosphate modified nickel-iron-manganese-based material.
In a seventh aspect, an embodiment of the present invention provides a sodium-ion secondary battery including the positive electrode tab of the above sixth aspect.
Preferably, the sodium ion secondary battery is used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power stations, backup power sources or communication base stations.
The invention provides a ferro-nickel-manganese-based layered oxide material with an aluminum phosphate/sodium phosphate modified surface, which is simple to prepare and contains non-toxic and safe elements such as sodium, nickel, iron and manganese. The nickel-iron-manganese-based layered oxide material with the surface modified by aluminum phosphate/sodium phosphate can effectively improve the cycling stability of the material. In a half-cell test, the capacity retention rate of the nickel-iron-manganese-based oxide material improved by the method in 200 weeks is improved by about 20%, and the nickel-iron-manganese-based oxide material has good cycle stability and great practical value. The sodium ion secondary battery based on the sodium nickel iron manganese based layered oxide material can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power sources or communication base stations.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
FIG. 1 is a flow chart of a method for preparing an aluminum phosphate/sodium phosphate modified surface Ni-Fe-Mn based layered oxide material by a solid phase method according to an embodiment of the present invention;
fig. 2 is a flowchart of a method for preparing an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based layered oxide material by a sol-gel method according to an embodiment of the present invention;
fig. 3 is a flowchart of a method for preparing a nickel-iron-manganese-based layered oxide material with an aluminum phosphate/sodium phosphate modified surface by a spray drying method according to an embodiment of the present invention;
fig. 4 is a flowchart of a co-precipitation method for preparing an aluminum phosphate/sodium phosphate modified surface nickel manganese iron-based layered oxide material according to an embodiment of the present invention;
FIG. 5 is an X-ray diffraction (XRD) pattern of nickel-iron-manganese-based layered oxide materials modified with different mole percentages of aluminum phosphate provided by embodiments of the present invention;
FIG. 6 is a 2-4V charging/discharging curve diagram of the sodium-ion battery provided in example 1 of the present invention;
FIG. 7 is a 200-cycle diagram of a sodium-ion battery at 2-4V, according to example 1 of the present invention;
fig. 8 is a charge-discharge curve diagram of the sodium ion battery provided in embodiment 1 of the present invention at 2-4.2V.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited thereto.
The invention provides a nickel-iron-manganese-based layered oxide material with an in-situ formed aluminum phosphate/sodium phosphate modified surface, a preparation method and application.
The material is a layered oxide material with space group of
In the nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface, aluminum phosphate formed in situ is distributed on the surface of a sodium-nickel-iron-manganese material, or distributed on the surface of the sodium-nickel-iron-manganese material and dispersed in a material body phase of the sodium-nickel-iron-manganese material; the sodium phosphate formed in situ is distributed on the surface of the sodium nickel iron manganese material. The aluminum phosphate/sodium phosphate formed in situ is decorated on the surface of the material, so that the side reaction can be reduced; formed by reaction with residual alkali on the surfaceThe sodium phosphate is used as a fast ion conductor of sodium, a channel is provided for the embedding and the separation of the sodium, the multiplying power performance can be effectively improved, and the air stability of the material is improved to a certain extent.
The chemical general formula of the nickel-iron-manganese-based material on the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4 @Na a [Ni b Fe c Mn d Me e ]O 2+β (ii) a Wherein, the valence of Ni is +2, the valence of Fe is +3, the valence of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4; a. b, c, d, e and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02.
The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is used as a positive electrode active material of a sodium ion secondary battery, when the nickel ion is charged for the first week, the nickel ion loses electrons, the valence state is changed from +2 valence to +3 valence, and meanwhile, the iron ion loses electrons, and the valence state is changed from +3 valence to +4 valence; during the first cycle of discharge, the nickel ions with higher valence state get electrons back to +2 valence state, and the iron ions get electrons back to +3 valence state.
The aluminum phosphate/sodium phosphate modified on the surface of the nickel-iron-manganese-based material does not participate in the oxidation-reduction reaction. The existence of the electrolyte reduces the corrosion of the electrolyte to the material, and protects the matrix structure of the electrode material.
The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface can be used for the positive pole piece of a sodium ion secondary battery. The sodium ion secondary battery using the lithium ion secondary battery as the positive pole piece can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power supplies or communication base stations.
The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface can be prepared by various methods.
Fig. 1 is a flow chart of a method for preparing an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based layered oxide material by a solid phase method according to an embodiment of the present invention. As shown in fig. 1, the main steps of the method include:
110, sodium carbonate with the stoichiometric quantity of 100 to 108 weight percent of the required sodium and NiO and Fe with the stoichiometric quantity of the required 2 O 3 And/or Fe 3 O 4 、Mn 2 O 3 And/or MnO 2 、MeO α/2 Mixing the raw materials into a precursor according to a certain proportion;
wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
preferably, alNO 3 ,(NH 4 ) 2 HPO 4 The dosage of the nickel-iron-manganese-based layered oxide is 0.01 to 5 percent of the total mole percentage of the nickel-iron-manganese-based layered oxide respectively.
and 150, grinding the heat-treated product to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
Fig. 2 is a flowchart of a method for preparing an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based layered oxide material by a sol-gel method according to an embodiment of the present invention. As shown in fig. 2, the main steps of the method include:
wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; α is more than or equal to +2 and less than or equal to +4;
specifically, the chelating agent may be specifically preferably used: ethylene glycol: citric acid = 4; the addition amount is citric acid: transition metal (Ni, fe, mn, me) molar ratio =1:1;
wherein, the evaporating temperature is as follows: 40-200 ℃, stirring speed is as follows: 100-1000r/min;
preferably, alNO 3 ,(NH 4 ) 2 HPO 4 The dosage of the nickel-iron-manganese-based layered oxide is 0.01 to 5 percent of the total mole percentage of the nickel-iron-manganese-based layered oxide respectively.
And 250, carrying out heat treatment at 600-1000 ℃ for 2-24 hours, and grinding the heat-treated powder to obtain the aluminum phosphate/sodium phosphate modified nickel-iron-manganese-based material.
Fig. 3 is a flowchart of a preparation method for preparing an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based layered oxide material by a spray drying method according to an embodiment of the present invention. As shown in fig. 3, the main steps of the method include:
wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
wherein, the evaporating temperature is as follows: stirring at 80-120 deg.c and 20-400r/min;
preferably, alNO 3 ,(NH 4 ) 2 HPO 4 The dosage of the nickel-iron-manganese-based layered oxide is 0.01 to 5 percent of the total mole percentage of the nickel-iron-manganese-based layered oxide respectively.
and 350, grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
Fig. 4 is a flowchart of a method for preparing an aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based layered oxide material by a coprecipitation method according to an embodiment of the present invention. As shown in fig. 4, the main steps of the method include:
wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
wherein, the concentration range of the ammonia water solution is as follows: 10% -28%; the pH value range is 10.0-12.0;
the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, a, b, c, d, e and beta are respectively the mole percentage occupied by the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
wherein, the heating temperature is as follows: at the temperature of 40-60 ℃, the stirring speed is as follows: 400-1000 r/min;
and step 450, grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
The above-mentioned several preparation methods can be used to prepare the aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material of the above-mentioned examples. The method provided by the embodiment is simple and easy to implement, has low cost, contains elements of phosphorus, aluminum, sodium, nickel, iron and manganese which are nontoxic and safe elements, and is suitable for large-scale manufacturing application. The characteristic peaks of the aluminum phosphate and the sodium phosphate formed in situ on the surface of the material can be measured by XRD test, and the generation of the material is proved. The aluminum phosphate and the sodium phosphate can effectively inhibit side reactions with the electrolyte. In a half-cell test, the nickel-iron-manganese-based layered oxide material improved by the method has better cycle life and great practical value. The sodium ion secondary battery based on the sodium nickel iron manganese based layered oxide material can be used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power sources or communication base stations.
In order to better understand the technical scheme provided by the invention, the following specific examples respectively illustrate the specific process for preparing the sodium nickel iron manganese based layered oxide material by using the methods provided by the above embodiments of the invention, and the method for applying the material to the sodium ion battery and the battery characteristics.
Example 1
In this embodiment, the solid phase method for preparing the sodium nickel iron manganese based layered oxide material includes:
mixing Na 2 CO 3 (analytically pure), niO (analytically pure), fe 2 O 3 (analytical pure), mnO 2 (analytically pure) mixing according to the required stoichiometric ratio; grinding in an agate mortar for half an hour to obtain precursor powder.
Dividing the precursor powder into 5 groups, and respectively mixing with AlNO in stoichiometric amount of 1%,2%,3%,4% and 5% of the total amount of the nickel-iron-manganese-based layered oxide in mol percentage 3 And (NH) 4 ) 2 HPO 4 Dispersing in absolute ethyl alcohol, heating, stirring and evaporating to dryness. Tabletting the product obtained after evaporation to dryness and transferring the product to Al 2 O 3 Treating in a crucible at 900 deg.C for 15 hr, and grinding to obtain 5-group black powder of layered oxide material AlPO 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 ，
For convenient recording, naNi is added 0.4 Fe 0.2 Mn 0.4 O 2 Denoted NFM. The XRD patterns of the materials of each group are shown in fig. 5. From XRD pattern, alPO 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 The crystal structure of (b) is an oxide of an O3 phase layered structure.
Limited by XRD measurement accuracy, can be 5% AlPO 4 The results of the test @ NFM showed that diffraction peaks for sodium phosphate were observed at 21 ℃ to 22 ℃ and around 34 ℃, indicating that sodium phosphate was formed by the reaction of the residual alkali on the surface.
1% AlPO obtained by the above-mentioned preparation 4 The @ NFM material is used for preparing the sodium-ion battery as an active substance of a battery positive electrode material, and the preparation method comprises the following specific steps: the prepared 1% AlPO 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 Mixing the powder with acetylene black and a polyvinylidene fluoride (PVDF) binder according to a mass ratio of 80Grinding to form slurry, uniformly coating the slurry on a current collector aluminum foil, drying under an infrared lamp, and cutting into (8 × 8) mm 2 The pole piece of (2). The pole piece is dried for 10 hours at 110 ℃ under vacuum condition and then transferred to a glove box for standby.
The assembly of the simulated cell was carried out in a glove box under Ar atmosphere, with sodium metal as the counter electrode and NaClO as the counter electrode 4 Propylene Carbonate (PC) and Ethylene Carbonate (EC) (EC: PC = 1) solutions were used as electrolytes to assemble CR2032 coin cells. The charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode. The test results are shown in FIG. 6 under the conditions of a discharge cutoff voltage of 2V and a charge cutoff voltage of 4V.
Simultaneously directly using NaNi 0.4 Fe 0.2 Mn 0.4 O 2 The material is used as an active substance of a battery anode material for preparing a sodium ion battery, and the specific steps are the same as above for comparison.
In FIG. 6, naNi is compared 0.4 Fe 0.2 Mn 0.4 O 2 (NFM in the figure) and 1% AlPO 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 (denoted as AlPO in the figure) 4 @ NFM) first week of Charge/discharge cycle curves, it can be seen that 1% AlPO was used in the present invention 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 The first cycle discharge specific capacity can reach 147mAh/g, and almost no capacity loss exists.
Fig. 7 is a 200-cycle diagram of the sodium ion battery provided in example 1 of the present invention at 2-4V. Capacity retention of the NFM material without surface modification at about 60% at 200 weeks, 1% 4 The capacity retention of the material @ NFM reaches about 80% at 200 weeks. The cycle stability is obviously improved.
The charge and discharge test was performed at a current density of C/10 using a constant current charge and discharge mode. The test results are shown in FIG. 8 for a discharge cutoff voltage of 2V and a charge cutoff voltage of 4.2V.
In FIG. 8, naNi is compared 0.4 Fe 0.2 Mn 0.4 O 2 (NFM in the figure) and 1mol% 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 (denoted as AlPO in the figure) 4 @ NFM), it can be seen that the 1mol% of AlPO was used in the present invention 4 @NaNi 0.4 Fe 0.2 Mn 0.4 O 2 The first cycle discharge specific capacity can reach 181mAh/g, and almost no capacity loss exists.
Example 2
In this embodiment, the preparation of the sodium nickel iron manganese-based layered oxide material by the coprecipitation method includes:
dissolving nitrate of Ni, nitrate of Fe, sulfate of Mn and sulfate of Mg in absolute ethyl alcohol according to a stoichiometric ratio to form a precursor solution;
dripping the precursor solution, ammonia water with the concentration of 18 percent and sodium hydroxide solution into a reaction kettle by a peristaltic pump to maintain the pH value of the reaction kettle to be 11 (the precision is 25 ℃), and generating a precipitate [ Ni 0.39 Mg 0.01 Fe 0.2 Mn 0.4 ]O 2 A precursor;
is prepared from [ Ni 0.39 Mg 0.01 Fe 0.2 Mn 0.4 ]O 2 Precursor, desired stoichiometry 105wt% Na 2 CO 3 3% of AlNO 3 3% NH 4 H 2 PO 4 Adding the mixture into water, heating and stirring until the mixture is dried, and drying to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 10 hours at 800 ℃ in an air atmosphere;
grinding the heat-treated precursor powder to obtain aluminum phosphate/sodium phosphate modified surface Ni-Fe-Mn based material with the percentage of 3mol percent AlPO 4 @[Ni 0.39 Mg 0.01 Fe 0.2 Mn 0.4 ]O 2 。
Example 3
In this embodiment, the spray drying method is used to prepare the sodium nickel iron manganese based layered oxide material, and includes:
104wt% of sodium carbonate and NiO and Fe with the required stoichiometric amount 2 O 3 、MnO 2 、TiO 2 Mixing the raw materials into a precursor according to a certain proportion;
adding absolute ethyl alcohol into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder;
mixing the precursor powder with 3mol% of AlNO 3 3mol% of (NH) 4 ) 2 HPO 4 Dispersing in deionized water, stirring and evaporating to dryness to obtain coated precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 12 hours at 1000 ℃ in an air atmosphere;
grinding the heat-treated precursor powder to obtain aluminum phosphate/sodium phosphate modified surface Ni-Fe-Mn based material with the percentage of 3mol percent AlPO 4 @[Ni 0.4 Fe 0.2 Mn 0.39 Ti 0.01 ]O 2 。
Example 4
In this embodiment, the preparation of the sodium nickel iron manganese based layered oxide material by the sol-gel method includes:
dissolving sodium acetate and sodium sulfate with the stoichiometric quantity of 108wt% of required sodium, nitrate of Ni, nitrate of Fe, sulfate of Mn and sulfate of Al in absolute ethyl alcohol to form precursor solution;
stirred at 50 ℃ and added with the appropriate amount of chelating agent ethylene glycol: citric acid =4, evaporated to dryness to form a precursor gel;
placing the precursor gel in a crucible, and presintering for 2 hours at 500 ℃ in an air atmosphere to obtain a precursor;
mixing the precursor with 3mol% of AlNO 3 3mol% of (NH) 4 ) 2 HPO 4 Dispersing in absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
heat treating at 600 deg.C for 24 hr, grinding the heat treated precursor powder to obtain aluminum phosphate/sodium phosphate modified surface Ni-Fe-Mn based material 3mol% 4 @Ni 0.4 Fe 0.19 Al 0.01 Mn 0.4 O 2 。
The nickel-iron-manganese-based layered oxide material with the aluminum phosphate/sodium phosphate modified surface is simple to prepare, and the contained elements, namely sodium, nickel, iron and manganese, are nontoxic and safe elements. The nickel-iron-manganese-based layered oxide material with the surface modified by the aluminum phosphate/sodium phosphate can effectively improve the circulation stability of the material. In a half-cell test, the capacity retention rate of the nickel-iron-manganese-based oxide material improved by the method in 200 weeks is improved by about 20%, and the nickel-iron-manganese-based oxide material has good cycle stability and great practical value. The sodium ion secondary battery based on the sodium nickel iron manganese based layered oxide material can be used for solar power generation, wind power generation, smart grid peak regulation, distributed power stations, backup power sources or large-scale energy storage equipment of communication base stations.
Claims (10)
1. The nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface is characterized by being a layered oxide material with a space group
In the material, the aluminum phosphate formed in situ is distributed on the surface of the NaNiFeMn material, or is distributed on the surface of the NaNiFeMn material and is dispersed in the material body phase of the NaNiFeMn material; the sodium phosphate formed in situ is distributed on the surface of the sodium-nickel-iron-manganese material;
the chemical general formula of the nickel-iron-manganese-based material on the aluminum phosphate/sodium phosphate modified surface is as follows: alPO 4 @Na a [Ni b Fe c Mn d Me e ]O 2+β ；
Wherein the valence of Ni is +2, the valence of Fe is +3, the valence of Mn is +4, me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4; a. b, c, d, e and beta are respectively the mol percentage of the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02.
2. The aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material as claimed in claim 1, wherein the aluminum phosphate/sodium phosphate modified surface nickel-iron-manganese-based material is used as a positive electrode active material of a sodium ion secondary battery, when charged for the first week, nickel ions lose electrons, the valence state is changed from +2 valence to +3 valence, and simultaneously iron ions lose electrons, the valence state is changed from +3 valence to +4 valence; during the first cycle of discharge, the nickel ions with higher valence state get electrons back to +2 valence state, and the iron ions get electrons back to +3 valence state.
3. The material as recited in claim 1, wherein the surface modified aluminum/sodium phosphate of the ni-fe-mn based material does not participate in the redox reaction.
4. A method of preparing an aluminum phosphate/sodium phosphate modified surface ni-fe-mn based material as recited in any one of claims 1 to 3, wherein the method comprises:
dissolving nitrates or sulfates of Ni, fe, mn and Me in water or absolute ethyl alcohol according to a stoichiometric ratio to form a precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
dripping the precursor solution into ammonia water solution with certain concentration and pH value by using a peristaltic pump to generate precipitate [ Ni b Fe c Mn d Me e ]O 2+β A precursor; wherein the valence state of Ni is +2, the valence state of Fe is +3, the valence state of Mn is +4, a, b, c, d, e and beta are respectively the mole percentage of the corresponding elements; the relationship between them satisfies b + c + d + e =1, and a +2b +3c +4d + α e =2 × (2 + β); wherein a is more than or equal to 0.8 and less than or equal to 1.0; b is more than 0 and less than or equal to 0.9; c is more than 0 and less than or equal to 0.33; d is more than 0 and less than or equal to 0.4; e is more than or equal to 0 and less than or equal to 0.33; beta is more than or equal to minus 0.02 and less than or equal to 0.02;
is prepared from [ Ni b Fe c Mn d Me e ]O 2+β Precursor, naOH and/or Na with the required stoichiometric quantity of 100wt% -108 wt% 2 CO 3 0.01mol% to 5mol% of AlNO 3 0.01mol% -5 mol% of NH 4 H 2 PO 4 And/or (NH) 4 ) 2 HPO 4 Adding into water or anhydrous ethanol, heating and stirring until drying, and drying to obtain precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
5. A method for preparing an aluminum/sodium phosphate modified surface ni-fe-mn based material as claimed in any one of claims 1 to 3, wherein the method comprises:
sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium and NiO and Fe with the stoichiometric quantity of the required 2 O 3 And/or Fe 3 O 4 、Mn 2 O 3 And/or MnO 2 、MeO α/2 Mixing the raw materials into a precursor according to a certain proportion; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
adding absolute ethyl alcohol or water into the precursor, and uniformly stirring to form slurry;
spray drying the slurry to obtain precursor powder; mixing the precursor powder with AlNO in required stoichiometric amount 3 ,NH 4 H 2 PO 4 And/or (NH) 4 ) 2 HPO 4 Dispersing in deionized water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain coated precursor powder;
placing the precursor powder in a muffle furnace, and carrying out heat treatment for 2-24 hours at 600-1000 ℃ in an air atmosphere;
and grinding the precursor powder after heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
6. A method for preparing an aluminum/sodium phosphate modified surface ni-fe-mn based material as claimed in any one of claims 1 to 3, wherein the method comprises:
dissolving one or more of sodium acetate, sodium nitrate, sodium carbonate and sodium sulfate with the stoichiometric amount of 100-108 wt% of the required sodium and nitrate or sulfate containing Ni, fe, mn and Me in water or absolute ethyl alcohol according to the stoichiometric ratio to form precursor solution; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; α is more than or equal to +2 and less than or equal to +4;
stirring at 50-100 ℃, adding a proper amount of chelating agent, and evaporating to dryness to form precursor gel;
placing the precursor gel in a crucible, and presintering for 2 hours at the temperature of 200-500 ℃ in the air atmosphere to obtain a precursor;
mixing the precursor with AlNO in required stoichiometric amount 3 ，NH 4 H 2 PO 4 And/or (NH) 4 ) 2 HPO 4 Dispersing in water or absolute ethyl alcohol, stirring and evaporating to dryness to obtain precursor powder;
and then carrying out heat treatment at 600-1000 ℃ for 2-24 hours, and grinding the heat-treated powder to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
7. A method for preparing an aluminum/sodium phosphate modified surface ni-fe-mn based material as claimed in any one of claims 1 to 3, wherein the method comprises:
sodium carbonate with the stoichiometric quantity of 100-108 wt% of the required sodium and NiO and Fe with the stoichiometric quantity of the required 2 O 3 And/or Fe 3 O 4 、Mn 2 O 3 And/or MnO 2 、MeO α/2 Mixing the components into a precursor in proportion; wherein Me is one or more elements of Mg, al and Ti, and the average valence of Me is alpha; +2 is not less than alpha and not more than +4;
uniformly mixing the precursors by adopting a ball milling method to obtain precursor powder;
mixing the precursor powder with AlNO in required stoichiometric amount 3 ,(NH 4 ) 2 HPO 4 Dispersing in absolute ethyl alcohol, heating, stirring and evaporating to dryness;
placing the product obtained after evaporation to dryness in a muffle furnace, and carrying out heat treatment for 2-24 hours in an air atmosphere at the temperature of 600-1000 ℃;
and grinding the product after the heat treatment to obtain the nickel-iron-manganese-based material with the aluminum phosphate/sodium phosphate modified surface.
8. A positive electrode plate of a sodium ion secondary battery, characterized in that the positive electrode plate comprises:
a current collector, a conductive additive and a binder coated on the current collector, and an aluminum/sodium phosphate modified surface nickel iron manganese based material as recited in any one of claims 1-3 above.
9. A sodium ion secondary battery comprising the positive electrode sheet as defined in claim 8.
10. The sodium ion secondary battery according to claim 9, wherein the sodium ion secondary battery is used for large-scale energy storage equipment of solar power generation, wind power generation, smart grid peak shaving, distributed power plants, backup power sources, or communication base stations.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117254020A (en) * | 2023-11-13 | 2023-12-19 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
| CN117276551A (en) * | 2023-11-23 | 2023-12-22 | 兰钧新能源科技有限公司 | Sodium-electricity layered oxide positive electrode material, preparation method thereof and sodium-ion battery |
| CN117476917A (en) * | 2023-12-28 | 2024-01-30 | 深圳先进技术研究院 | Positive electrode material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117254020A (en) * | 2023-11-13 | 2023-12-19 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
| CN117254020B (en) * | 2023-11-13 | 2024-03-08 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
| CN117276551A (en) * | 2023-11-23 | 2023-12-22 | 兰钧新能源科技有限公司 | Sodium-electricity layered oxide positive electrode material, preparation method thereof and sodium-ion battery |
| CN117276551B (en) * | 2023-11-23 | 2024-03-19 | 兰钧新能源科技有限公司 | Sodium-electricity layered oxide positive electrode material, preparation method thereof and sodium-ion battery |
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