CN116404154A - High-entropy sodium ferric pyrophosphate sodium ion battery anode material and preparation method thereof - Google Patents

High-entropy sodium ferric pyrophosphate sodium ion battery anode material and preparation method thereof Download PDF

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CN116404154A
CN116404154A CN202310334374.6A CN202310334374A CN116404154A CN 116404154 A CN116404154 A CN 116404154A CN 202310334374 A CN202310334374 A CN 202310334374A CN 116404154 A CN116404154 A CN 116404154A
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sodium
ion battery
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杨成浩
陈昌东
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/38—Condensed phosphates
    • C01B25/42—Pyrophosphates
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
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    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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    • Y02E60/10—Energy storage using batteries

Abstract

The invention belongs to the technical field of sodium ion battery anode materials, and discloses a high-entropy ferric sodium pyrophosphate ion battery anode material and a preparation method thereof, wherein the anode material is formed by taking ferric sodium pyrophosphate particles as cores and coating surface carbon; the chemical formula is Na 4 Fe 3‑x‑y‑z‑α‑β Mg x Ca y Al z Cr α Mn β (PO 4 )(P 2 O 7 ) X is more than or equal to 0.01 and less than or equal to 0.1, y is more than or equal to 0.01 and less than or equal to 0.1, z is more than or equal to 0.01 and less than or equal to 0.1, alpha is more than or equal to 0.01 and less than or equal to 0.1, and beta is more than or equal to 0.01 and less than or equal to 0.1; the preparation method comprises the following steps: s1, preparing a solution A containing magnesium, calcium, aluminum, chromium, manganese, iron and ethylene glycol; s2, preparing a mixture containing sodium, phosphorus, carbon and auxiliary agentSolution B of agent; s3, dropwise adding the A into the B to obtain a suspension C; s4, stirring, heating, evaporating to dryness, drying overnight and ball milling the C to obtain a positive electrode precursor; s5, sintering the positive electrode precursor, cooling, crushing, grinding and screening; the high-entropy sodium ion battery anode material obtained by the invention has the advantages of single phase, good crystallinity, uniform particle size and excellent electrochemical performance.

Description

High-entropy sodium ferric pyrophosphate sodium ion battery anode material and preparation method thereof
Technical Field
The invention relates to the technical field of sodium ion battery anode materials, in particular to a high-entropy ferric sodium pyrophosphate sodium ion battery anode material and a preparation method thereof.
Background
In recent years, energy storage technologies represented by lithium ion batteries are widely used in the fields of portable electronic devices, energy storage power stations, electric automobiles and the like, so that the yield and consumption of the lithium ion batteries are rapidly increased. However, the limited lithium resources cannot meet the market demand of lithium ion electromagnetic rapid expansion, and therefore, development of a novel energy storage device is particularly important. Related researches show that the sodium ion battery and the lithium ion battery have similar electrochemical reaction mechanisms, and are hopeful to become one of the most potential alternatives in the application field of the energy storage device. However, sodium ions are about 55% larger than lithium ions, so that the intercalation and diffusion of sodium ions in the same structural material are relatively difficult, and the structural change of the intercalated material is larger, so that the specific capacity, the dynamic performance, the cycle performance and the like of the electrode material are correspondingly deteriorated. Compared with the field of lithium ion batteries, the technical problem in the field of sodium ion batteries is solved, and the technical maturity of the sodium ion batteries is seriously delayed from that of the lithium ion batteries.
In addition, the cost is a core element for promoting the competition between the sodium ion battery and the lithium ion battery, and the ferric sodium pyrophosphate positive electrode material represented by the iron-based polyanion has low cost and excellent cycle performance, and becomes one of ideal choices for constructing the low-cost commercial sodium ion battery. However, due to the poor conductivity and electrochemical properties of sodium ferric pyrophosphate phosphate, the energy density is low and the cycle life is short. Therefore, researchers develop a series of modification strategies to solve the problem, wherein the high-entropy concept is widely applied to a structural design system of an electrochemical energy storage material, the high-entropy material is a material which contains 5 or more elements and is obtained by mutually solutionizing at an equimolar ratio or a near molar ratio and has a single phase, the unique configuration and electrochemical adjustability bring new opportunities for breaking through the performance bottleneck of the current electrode material, and the research on improving the multiplying power performance and the cycling stability of the sodium ferric pyrophosphate electrode material by utilizing the high-entropy material 'cocktail effect' is not reported.
Disclosure of Invention
The invention aims to provide a high-entropy ferric sodium pyrophosphate ion battery anodeAccording to the material and the preparation method, five elements Mg, ca, al, cr, mn with equal molar ratio form a combined crystal at the Fe position, and the diversified local structure well delays Na + Phase change reaction and charge compensation in the de-intercalation reaction of (2) effectively inhibit simple Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) The phase change reaction in the charge and discharge process stabilizes the matrix structure; obtaining the high-entropy sodium ion battery anode material Na 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) The material has single phase, good crystallinity and uniform particle size, and has excellent electrochemical performance in sodium ion batteries.
In order to achieve the above object, the present invention provides the following technical solutions:
the high-entropy ferric sodium pyrophosphate ion battery positive electrode material is formed by taking ferric sodium pyrophosphate particles as cores and coating surface carbon of the ferric sodium pyrophosphate particles; the chemical formula of the sodium ferric pyrophosphate is Na 4 Fe 3-x-y-z-α-β Mg x Ca y Al z Cr α Mn β (PO 4 )(P 2 O 7 )，0.01≤x≤0.1，0.01≤y≤0.1，0.01≤z≤0.1，0.01≤α≤0.1，0.01≤β≤0.1。
The preparation method of the high-entropy sodium ferric pyrophosphate sodium ion battery anode material comprises the following steps:
s1, preparing an aqueous solution A containing a magnesium source, a calcium source, an aluminum source, a chromium source, a manganese source, an iron source and ethylene glycol;
s2, preparing an aqueous solution B containing a sodium source, a phosphorus source, a carbon source and an auxiliary agent;
s3, slowly dripping the aqueous solution A into the aqueous solution B to obtain a suspension C;
s4, stirring, heating, evaporating to dryness, drying and ball milling the suspension C overnight to obtain a positive electrode precursor;
and S5, sintering the anode precursor in a protective atmosphere, cooling, crushing, grinding and screening to obtain the surface carbon-coated high-entropy sodium ferric pyrophosphate sodium ion battery anode material.
Further, in S1, the molar ratio of Fe element, mg element, ca element, al element, cr element and Mn element in the solution A is 2.95-3:0.01-0.1:0.01-0.1; the mass of the ethylene glycol accounts for 0.2 to 0.5 percent of the mass of the positive electrode material of the finished sodium iron pyrophosphate ion battery.
Further, in S1, the magnesium source is one or more mixtures of magnesium acetate, magnesium nitrate and hydrates thereof; the calcium source is one or more of calcium acetate, calcium nitrate and their hydrates; the aluminum source is one or a mixture of more of aluminum acetate, aluminum nitrate and hydrate thereof; the chromium source is one or a mixture of more of chromium acetate, chromium nitrate and hydrates thereof; the manganese source is one or a mixture of more of manganese acetate, manganese nitrate and hydrates thereof; the iron source is one or more of ferrous acetate, ferrous nitrate, ferric acetate and their hydrates.
Further, in S2, the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium oxalate, sodium citrate, sodium tartrate, sodium alginate, and sodium lactate; the phosphorus source is one or a mixture of more of sodium pyrophosphate, sodium dihydrogen pyrophosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate and diammonium hydrogen phosphate; the carbon source is any one or a mixture of more than one of glucose, lactose, fructose, oxalic acid, citric acid and sucrose; the auxiliary agent is any one or a mixture of more of ethanolamine, triethanolamine hydrochloride, lactic acid and sodium lactate.
Further, in S2, the mass of the carbon source accounts for 1-15% of the mass of the positive electrode material of the finished sodium iron phosphate sodium ion battery; the mass of the auxiliary agent accounts for 0.2 to 0.5 percent of the mass of the positive electrode material of the finished sodium ferric pyrophosphate sodium ion battery.
Further, in S3, the molar ratio of Na element, fe element, mg element, ca element, al element, cr element, mn element, phosphate radical and pyrophosphate radical in the suspension C is 3.95-4.05:2.95-3:0.01-0.1:0.01-0.1:2:1.
Further, in S4, the method of stirring the suspension C is: under the condition of the temperature of 10-60 ℃, stirring magnetically for 1-12 h at the stirring speed of 200-600 r/min to obtain a uniformly mixed solution.
Further, in S4, the heating and evaporating manner is as follows: the uniformly mixed solution is kept warm by a rotary evaporator at the temperature of 60-120 ℃ until water is completely evaporated, so as to obtain uniformly mixed powder; the ball milling conditions are as follows: ball milling speed is 150-600 r/min, and the bead ratio is 3-10: 1.
further, in S5, the protective atmosphere is nitrogen, argon or one or two mixed gases of inert atmosphere and reducing gas; the sintering temperature is heated to 200-350 ℃ at a heating rate of 2-10 ℃/min, presintered for 3-10 h, and sintered for 6-15 h at a temperature of 450-650 ℃ at a heating rate of 2-10 ℃/min.
The technical proposal has the beneficial effects that:
1. the invention provides a Na 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) The high-entropy sodium ion battery anode material has single phase, good crystallinity and uniform particle size, and has excellent electrochemical performance in sodium ion batteries;
2. according to the invention, five elements of Mg, ca, al, cr, mn with equal molar ratio form a combined crystal at Fe position, and the diversified local structure well delays Na + Phase change reaction and charge compensation in the de-intercalation reaction of (2) effectively inhibit simple Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) The phase change reaction in the charge and discharge process stabilizes the matrix structure; after 500 weeks of cyclic charge and discharge at the rate of 10C, the capacity retention rate of the material is 85.5%, which shows that the entropy effect well improves the cyclic stability of the material;
3. in the preparation of Na 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) In the process of the high-entropy sodium ion battery anode material,the auxiliary agent is favorable for forming stable metal chelate, and the glycol aqueous solution well improves the agglomeration of the material and improves the electrochemical performance of the material;
4. the invention prepares Na 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) The method for synthesizing the high-entropy sodium ion battery anode material is simple, is easy to industrialize, is environment-friendly and low in cost, avoids the use of harmful chemical reagents and the waste of equipment, and is easy for batch industrial application.
Drawings
FIG. 1 shows a high entropy sodium ferric pyrophosphate ion battery anode material Na prepared in example 1 of the present invention 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) SEM images of (a).
FIG. 2 is a high entropy sodium ferric pyrophosphate ion battery anode material Na prepared in example 1 of the present invention 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) Is a XRD pattern of (C).
FIG. 3 is a high entropy sodium ferric pyrophosphate ion battery anode material Na prepared in example 1 of the present invention 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) 0.1C charge-discharge curve.
FIG. 4 shows a high entropy sodium ferric pyrophosphate ion battery anode material Na prepared in example 1 of the present invention 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) Is a cycle performance chart of (c).
Detailed Description
The invention is described in further detail below with reference to the attached drawings and embodiments:
example 1
The preparation method of the high-entropy sodium ferric pyrophosphate sodium ion battery anode material comprises the following steps:
s1, respectively weighing 0.00005mol of magnesium nitrate nonahydrate, 0.00005mol of calcium nitrate tetrahydrate, 0.00005mol of aluminum nitrate nonahydrate, 0.00005mol of chromium nitrate nonahydrate, 0.00005mol of manganese nitrate tetrahydrate, 0.01475mol of ferric nitrate nonahydrate and 4g of glycol, adding 200ml of distilled water, and setting stirring speed at room temperature for 250r/min for 1h to prepare an aqueous solution A;
s2, weighing 0.005mol of sodium pyrophosphate, 0.01mol of ammonium dihydrogen phosphate, 3g of glucose and 4g of triethanolamine, adding 200ml of distilled water, and setting stirring speed at room temperature for 1h at 250r/min to obtain an aqueous solution B;
s3, dropwise adding the aqueous solution A into the aqueous solution B, and setting stirring speed at room temperature for 1h at 250r/min to obtain suspension C;
s4: evaporating the suspension C at 80 ℃ and at a stirring speed of 350r/min, drying overnight, and ball-milling to obtain a positive electrode precursor;
s5: pre-sintering the positive electrode precursor obtained in the step S4 for 8 hours at 300 ℃ under the nitrogen atmosphere and with the heating rate of 2 ℃/min, then sintering for 12 hours at 500 ℃, cooling, crushing and grinding to obtain the Na with the surface carbon coating 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 )(P 2 O 7 ) High entropy sodium ferric pyrophosphate sodium ion battery anode material.
As shown in FIG. 1, the high entropy sodium ferric pyrophosphate sodium ion battery anode material Na prepared by the method is 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) SEM images of (a);
as shown in FIG. 2, the high entropy sodium ferric pyrophosphate sodium ion battery anode material Na prepared by the method is 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 ) 2 (P 2 O 7 ) An XRD pattern of (a);
8:1:1, the prepared material, the conductive agent acetylene black and the binder PVDF are weighed according to the weight ratio, 0.1g is uniformly mixed with N-methyl pyrrolidone, then the mixture is coated on the surface of an aluminum foil, the cut mixture is used as an anode, sodium metal is used as a cathode, and 1mol/LNaClO is used as a cathode 4 EC: DEC (volume ratio 1:1)/5.0% FEC is electrolyte, and assembled into button cell, as shown in FIG. 3 and FIG. 4, the electrochemical performance test shows that the obtained Na 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 )(P 2 O 7 ) The high-entropy ferric sodium pyrophosphate material is used in a sodium ion battery positive electrode material, and has a specific capacity of 118.6mAh/g after initial discharge at a rate of 0.1C and a capacity retention rate of 85.5% after cyclic charge and discharge for 500 weeks at a rate of 10C.
Example 2
The preparation method of the high-entropy sodium ferric pyrophosphate sodium ion battery anode material comprises the following steps:
s1, respectively weighing 0.00004mol of magnesium acetate tetrahydrate, 0.00004mol of calcium nitrate tetrahydrate, 0.00004mol of aluminum nitrate nonahydrate, 0.00004mol of chromium nitrate nonahydrate, 0.00004mol of manganese nitrate tetrahydrate, 0.0118mol of ferrous acetate and 4g of glycol, adding 200ml of distilled water, and setting stirring speed at room temperature for 250r/min for 1h to prepare an aqueous solution A;
s2, weighing 0.004mol of sodium dihydrogen pyrophosphate, 0.008mol of diammonium hydrogen phosphate, 2.4g of lactose and 5g of sodium lactate, adding 200ml of distilled water, and setting stirring speed at room temperature for 250r/min for 1h to prepare an aqueous solution B;
s3, dropwise adding the aqueous solution A into the aqueous solution B, and setting stirring speed at room temperature for 1h at 250r/min to obtain suspension C;
s4, evaporating the suspension C at the temperature of 80 ℃ and the stirring speed of 350r/min, drying overnight, and ball milling to obtain a positive electrode precursor;
s5, pre-sintering the positive electrode precursor obtained in the step S4 for 10 hours at the temperature of 280 ℃ under the nitrogen atmosphere at the heating rate of 2 ℃/min, and thenSintering at 550 deg.c for 10 hr, cooling, crushing and grinding to obtain surface carbon coated Na 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 )(P 2 O 7 ) High entropy sodium ferric pyrophosphate sodium ion battery anode material.
The material prepared in the embodiment is prepared into a positive electrode plate by the same method as in the embodiment 1, and is used as a positive electrode material for a sodium ion battery for testing, and the obtained high-entropy ferric sodium phosphate composite material is high in specific capacity and good in cycling stability as the positive electrode material, and shows excellent electrochemical performance.
Example 3
The preparation method of the high-entropy sodium ferric pyrophosphate sodium ion battery anode material comprises the following steps:
s1, respectively weighing 0.00007mol of magnesium acetate tetrahydrate, 0.00007mol of calcium acetate monohydrate, 0.00007mol of aluminum nitrate nonahydrate, 0.00007mol of chromium acetate, 0.00007mol of manganese acetate tetrahydrate, 0.02065mol of ferrous acetate and 10g of ethylene glycol, adding 200ml of distilled water, and setting stirring speed at room temperature for 250r/min for 1h to prepare an aqueous solution A;
s2, weighing 0.007mol of sodium dihydrogen pyrophosphate, 0.014mol of diammonium hydrogen phosphate, 4g of lactose and 10g of triethanolamine hydrochloride, adding 200ml of distilled water, and setting stirring speed at room temperature for 250r/min for 1h to prepare an aqueous solution B;
s3, dropwise adding the aqueous solution A into the aqueous solution B, and setting stirring speed at room temperature for 1h at 250r/min to obtain suspension C;
s4, evaporating the suspension C at the temperature of 80 ℃ and the stirring speed of 350r/min, drying overnight, and ball milling to obtain a positive electrode precursor;
s5, pre-sintering the positive electrode precursor obtained in the step S4 for 3 hours at the temperature of 350 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, then sintering for 12 hours at the temperature of 500 ℃, cooling, crushing and grinding to obtain the Na with the surface carbon coating 4 Fe 2.95 Mg 0.01 Ca 0.01 Al 0.01 Cr 0.01 Mn 0.01 (PO 4 )(P 2 O 7 ) High entropy ferric pyrophosphateSodium-sodium ion battery positive electrode material.
The foregoing is merely exemplary embodiments of the present invention, and detailed technical solutions or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present invention, and these should also be regarded as the protection scope of the present invention, which does not affect the effect of the implementation of the present invention and the practical applicability of the patent. The protection scope of the present application shall be subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.

Claims (10)

1. A high entropy phosphoric acid ferric sodium pyrophosphate sodium ion battery anode material is characterized in that: the positive electrode material is formed by coating surface carbon of sodium ferric phosphate granules serving as cores; the chemical formula of the sodium ferric pyrophosphate is Na 4 Fe 3-x-y-z-α-β Mg x Ca y Al z Cr α Mn β (PO 4 )(P 2 O 7 )，0.01≤x≤0.1，0.01≤y≤0.1，0.01≤z≤0.1，0.01≤α≤0.1，0.01≤β≤0.1。
2. The preparation method of the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 1, which is characterized by comprising the following steps:
s1, preparing an aqueous solution A containing a magnesium source, a calcium source, an aluminum source, a chromium source, a manganese source, an iron source and ethylene glycol;
s2, preparing an aqueous solution B containing a sodium source, a phosphorus source, a carbon source and an auxiliary agent;
s3, slowly dripping the aqueous solution A into the aqueous solution B to obtain a suspension C;
s4, stirring, heating, evaporating to dryness, drying and ball milling the suspension C overnight to obtain a positive electrode precursor;
and S5, sintering the anode precursor in a protective atmosphere, cooling, crushing, grinding and screening to obtain the surface carbon-coated high-entropy sodium ferric pyrophosphate sodium ion battery anode material.
3. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S1, the molar ratio of Fe element, mg element, ca element, al element, cr element and Mn element in the solution A is 2.95-3:0.01-0.1:0.01-0.1; the mass of the ethylene glycol accounts for 0.2 to 0.5 percent of the mass of the positive electrode material of the finished sodium iron pyrophosphate ion battery.
4. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S1, the magnesium source is one or a mixture of more of magnesium acetate, magnesium nitrate and hydrate thereof; the calcium source is one or more of calcium acetate, calcium nitrate and their hydrates; the aluminum source is one or a mixture of more of aluminum acetate, aluminum nitrate and hydrate thereof; the chromium source is one or a mixture of more of chromium acetate, chromium nitrate and hydrates thereof; the manganese source is one or a mixture of more of manganese acetate, manganese nitrate and hydrates thereof; the iron source is one or more of ferrous acetate, ferrous nitrate, ferric acetate and their hydrates.
5. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S2, the sodium source is one or more of sodium carbonate, sodium bicarbonate, sodium nitrate, sodium oxalate, sodium citrate, sodium tartrate, sodium alginate and sodium lactate; the phosphorus source is one or a mixture of more of sodium pyrophosphate, sodium dihydrogen pyrophosphate, ammonium dihydrogen phosphate, sodium dihydrogen phosphate and diammonium hydrogen phosphate; the carbon source is any one or a mixture of more than one of glucose, lactose, fructose, oxalic acid, citric acid and sucrose; the auxiliary agent is any one or a mixture of more of ethanolamine, triethanolamine hydrochloride, lactic acid and sodium lactate.
6. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S2, the mass of the carbon source accounts for 1-15% of the mass of the positive electrode material of the finished sodium ferric pyrophosphate sodium ion battery; the mass of the auxiliary agent accounts for 0.2 to 0.5 percent of the mass of the positive electrode material of the finished sodium ferric pyrophosphate sodium ion battery.
7. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S3, the molar ratio of Na element, fe element, mg element, ca element, al element, cr element, mn element, phosphate radical and pyrophosphate radical in the suspension C is 3.95-4.05:2.95-3:0.01-0.1:0.01-0.1:2:1.
8. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S4, the method of stirring the suspension C is: under the condition of the temperature of 10-60 ℃, stirring magnetically for 1-12 h at the stirring speed of 200-600 r/min to obtain a uniformly mixed solution.
9. The method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S4, the heating and evaporating manner is as follows: the uniformly mixed solution is kept warm by a rotary evaporator at the temperature of 60-120 ℃ until water is completely evaporated, so as to obtain uniformly mixed powder; the ball milling conditions are as follows: ball milling speed is 150-600 r/min, and the bead ratio is 3-10: 1.
10. the method for preparing the high-entropy sodium ferric phosphate sodium ion battery positive electrode material according to claim 2, which is characterized in that: in S5, the protective atmosphere is one or two mixed gases of nitrogen, argon or inert atmosphere and reducing gas; the sintering temperature is heated to 200-350 ℃ at a heating rate of 2-10 ℃/min, presintered for 3-10 h, and sintered for 6-15 h at a temperature of 450-650 ℃ at a heating rate of 2-10 ℃/min.
CN202310334374.6A 2023-03-31 2023-03-31 High-entropy sodium ferric pyrophosphate sodium ion battery anode material and preparation method thereof Pending CN116404154A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117497753A (en) * 2023-12-29 2024-02-02 宁波容百新能源科技股份有限公司 Potassium-sodium mixed cathode material and preparation method and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107069012A (en) * 2017-04-24 2017-08-18 国网河南省电力公司电力科学研究院 Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof
CN108123129A (en) * 2018-01-04 2018-06-05 中南大学 A kind of carbon coating ferric sodium pyrophosphate material and preparation method thereof and the application as sodium-ion battery positive material
CN113104828A (en) * 2021-03-19 2021-07-13 三峡大学 Preparation method of porous carbon modified sodium iron pyrophosphate phosphate/sodium carbonate ion battery positive electrode material
CN114538403A (en) * 2022-01-27 2022-05-27 上海交通大学 Preparation method and application of sodium ion battery positive electrode material ferric sodium phosphate pyrophosphate
CN114715869A (en) * 2022-03-22 2022-07-08 华南理工大学 High-entropy metal phosphate with NASICON structure, and preparation method and application thereof
CN115360340A (en) * 2022-09-23 2022-11-18 北京理工大学 Anion-cation functionalized doped modified high-entropy polyanion type positive electrode material, preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107069012A (en) * 2017-04-24 2017-08-18 国网河南省电力公司电力科学研究院 Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof
CN108123129A (en) * 2018-01-04 2018-06-05 中南大学 A kind of carbon coating ferric sodium pyrophosphate material and preparation method thereof and the application as sodium-ion battery positive material
CN113104828A (en) * 2021-03-19 2021-07-13 三峡大学 Preparation method of porous carbon modified sodium iron pyrophosphate phosphate/sodium carbonate ion battery positive electrode material
CN114538403A (en) * 2022-01-27 2022-05-27 上海交通大学 Preparation method and application of sodium ion battery positive electrode material ferric sodium phosphate pyrophosphate
CN114715869A (en) * 2022-03-22 2022-07-08 华南理工大学 High-entropy metal phosphate with NASICON structure, and preparation method and application thereof
CN115360340A (en) * 2022-09-23 2022-11-18 北京理工大学 Anion-cation functionalized doped modified high-entropy polyanion type positive electrode material, preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117497753A (en) * 2023-12-29 2024-02-02 宁波容百新能源科技股份有限公司 Potassium-sodium mixed cathode material and preparation method and application thereof

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