CN112768673A - Na4Fe3-x(PO4)2P2O7Positive electrode material of/C sodium ion battery and preparation method and application thereof - Google Patents

Na4Fe3-x(PO4)2P2O7Positive electrode material of/C sodium ion battery and preparation method and application thereof Download PDF

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CN112768673A
CN112768673A CN202110171331.1A CN202110171331A CN112768673A CN 112768673 A CN112768673 A CN 112768673A CN 202110171331 A CN202110171331 A CN 202110171331A CN 112768673 A CN112768673 A CN 112768673A
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sodium
iron
source compound
acid
ferric
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曹余良
赵阿龙
袁天赐
周喜
艾新平
杨汉西
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Shenzhen Jana Energy Technology Co ltd
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Wuhan University WHU
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Abstract

The invention discloses Na4Fe3‑x(PO4)2P2O7Positive electrode material of/C sodium ion battery anda preparation method and application thereof. The anode material is Na4Fe3‑x(PO4)2P2O7And C, wherein Na4Fe3‑x(PO4)2P2O7Middle, 0<x<0.5, iron defects were present. The composite material is prepared by mixing and calcining raw materials of a sodium source, an iron source, a phosphorus source, a carbon source and a reducing agent, wherein the molar ratio of sodium to iron in the raw materials is controlled to be 4: (3-x), 0<x<0.5. The cathode material is obtained by simply preparing the cathode material by introducing iron defects from the structure and only reducing the content of iron sources in raw materials without new raw materials and additional synthesis processes, has little influence on the existing manufacturing process, high product purity, good crystallinity and high ionic and electronic conductivity, greatly improves the specific capacity and rate capability of the cathode material, and is suitable for large-scale production and application.

Description

Na4Fe3-x(PO4)2P2O7Positive electrode material of/C sodium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the field of sodium ion battery materials, and particularly relates to Na4Fe3-x(PO4)2P2O7A/C sodium ion battery positive electrode material, a preparation method and application thereof.
Background
In recent years, global problems such as fossil fuel shortage, environmental pollution and the like are increasingly serious, and people are urgently required to develop clean energy such as solar energy, wind energy, water energy and the like. However, these clean energy sources have the disadvantages of large fluctuation, poor stability, intermittent supply, etc., and need to be integrated and converted by a large-scale energy storage device for reasonable utilization. In the existing energy storage technology, a secondary battery is considered as one of ideal choices for large-scale energy storage technology due to its strong flexibility and high energy conversion efficiency. Although lithium ion batteries have met with great success in the field of portable electronic devices and electric vehicles due to their high energy density and good cycling stability, they cannot meet the inexpensive requirements for large-scale energy storage due to the lack and uneven distribution of lithium resources. However, the sodium ion battery has a similar working principle as the lithium ion battery, and has richer reserves and wider distribution. Considering the important property that the cost of large-scale energy storage devices is greater than the energy density, sodium ion batteries are considered as one of the potential candidates for large-scale energy storage systems.
At present there are alreadyA large number of sodium-ion battery positive electrode materials are reported, and only a few of the materials show good electrochemical properties, such as vanadium-based phosphates, iron-based phosphates, and prussian blue analogues. Also, these materials face serious problems in the course of commercialization of laboratory results, such as high toxicity and high cost of vanadium-based materials, structural instability of prussian blue analogues. Among iron-based phosphates, iron sodium pyrophosphate phosphate (Na)4Fe3(PO4)2P2O7) The advantages of all iron-based phosphates are combined: low cost, environment friendship and high theoretical capacity (129mAh g)-1) High average operating voltage (3.1vs. na)+Na) and low volume expansion (4% less), are considered to be the most potential positive electrode materials for sodium-ion batteries. However, the theoretical stoichiometric ratio of the sodium source and the iron source is 4:3 in the conventional method, and the stoichiometric ratio of Na is synthesized4Fe3(PO4)2P2O7Always accompanied by NaFePO4The generation of impurities seriously affects the capacity and rate capability of the material, and the Na synthesized by the conventional method4Fe3(PO4)2P2O7The crystallinity is poor and cannot meet the application requirements.
Disclosure of Invention
The invention aims to provide Na4Fe3-x(PO4)2P2O7A/C sodium ion battery positive electrode material, a preparation method and application thereof. The sodium ion battery anode material introduces iron defects from the structure, can be simply prepared by reducing the content of iron sources in raw materials, does not need new raw materials and additional synthesis process, has little influence on the existing manufacturing process, is easy to control, and the prepared Na has little influence on the existing manufacturing process4Fe3(PO4)2P2O7the/C has high purity, good crystallinity and high ionic and electronic conductivity, greatly improves the specific capacity and rate capability of the anode material, and is suitable for large-scale production and application.
In order to achieve the above purpose, the invention specifically provides the following technical scheme:
providing a Na4Fe3-x(PO4)2P2O7The positive electrode material of the sodium-ion battery is Na4Fe3-x(PO4)2P2O7And C, wherein Na4Fe3-x(PO4)2P2O7Middle, 0<x<0.5, iron defects were present.
According to the scheme, in the positive electrode material, Na4Fe3-x(PO4)2P2O7The mass ratio of C to C is 9.5:0.5-9.9: 0.1.
According to the scheme, 0.05< x < 0.15.
According to the scheme, the sodium-ion battery positive electrode material is prepared by mixing and calcining raw materials including a sodium source compound, an iron source compound, a phosphorus source compound, a carbon source compound and a reducing agent, wherein the molar ratio of sodium to iron in the raw materials is controlled to be 4: (3-x), 0< x < 0.5.
Providing a Na4Fe3-x(PO4)2P2O7The preparation method of the positive electrode material of the/C sodium-ion battery comprises the following steps:
(1) uniformly mixing raw materials of a sodium source compound, an iron source compound, a phosphorus source compound, a carbon source compound and a reducing agent, and fully drying to obtain a mixed raw material, wherein the molar ratio of sodium to iron in the mixed raw material is 4: (3-x), 0< x < 0.5;
(2) placing the mixed raw material in the step (1) in an inert atmosphere or a reducing atmosphere, and preserving the heat for 4-20 hours at the temperature of 350-4Fe3-x(PO4)2P2O7the/C sodium ion battery positive electrode material.
According to the scheme, in the step (1), the molar ratio of sodium to phosphorus elements is 1:1, the molar ratio of the carbon source compound to the iron source compound is (0.1-5):1, and the molar ratio of the reducing agent to the iron source compound is (0.1-5): 1.
According to the scheme, the iron source compound is one or more of iron powder, ferric citrate, ferrous citrate, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferroferric oxide, ferric oxide, ferrous oxide, ferric oxalate, ferrous oxalate, ferric acetate, ferric phosphate, ferric pyrophosphate and ferrous ammonium sulfate.
According to the scheme, the phosphorus source compound is one or more of sodium dihydrogen phosphate, sodium monohydrogen phosphate, phosphoric acid, ammonium dihydrogen phosphate, triammonium phosphate, pyrophosphoric acid, sodium pyrophosphate and sodium dihydrogen pyrophosphate.
According to the scheme, the sodium source compound is one or more of sodium dihydrogen phosphate, sodium carbonate, sodium nitrate, sodium oxalate, sodium acetate, sodium sulfate, sodium hydroxide, sodium formate, sodium citrate, sodium pyrophosphate and sodium dihydrogen pyrophosphate.
According to the scheme, the reducing agent is one or more of oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butyl aldehyde, lactic acid, citric acid, malic acid, oxalic acid, adipic acid, citric acid, soluble starch, ascorbic acid, sucrose and glucose.
According to the scheme, the carbon source compound is one or more of oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butyl aldehyde, lactic acid, citric acid, malic acid, oxalic acid, adipic acid, citric acid, soluble starch, ascorbic acid, sucrose and glucose.
According to the above scheme, the carbon source compound and the reducing agent may be the same or different.
According to the scheme, in the step (1), the raw material mixing method is one or two of ball milling and aqueous solution dissolution.
According to the scheme, in the step (1), the drying method of the mixture raw material is one or more of forced air drying, vacuum drying, freeze drying and spray drying.
According to the scheme, the inert atmosphere is nitrogen or argon; the reducing atmosphere is nitrogen-hydrogen mixed gas or argon-hydrogen mixed gas.
Providing the above Na4Fe3-x(PO4)2P2O7The application of the/C sodium ion battery positive electrode material in the sodium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention is Na in the positive electrode material of the sodium-ion battery4Fe3(PO4)2P2O7Iron defects are introduced into the structure, and the iron defects can distort chemical bonds among other elements, so that a diffusion channel of sodium ions is widened, the transmission speed of the sodium ions in the charging and discharging processes is improved, and the ionic conductivity of the positive electrode material is improved; iron defects can also change the electron cloud distribution of P, O and other elements, so that the electron conductivity of the positive electrode material is improved; the positive electrode material has higher ion conductivity and electronic conductivity, and the electrochemical reaction kinetics of the material are improved, so that the specific capacity and the rate capability of the positive electrode material are greatly improved.
2. The invention can introduce iron impurity into the structure and greatly reduce Na by only reducing the content of iron during synthesis and ensuring that the stoichiometric ratio of sodium to iron in the raw materials is more than 4:34Fe3(PO4)2P2O7NaFePO of (III)4Impurities and increase the crystallinity of the material; the preparation method is simple and controllable, no new raw materials and additional synthesis process are needed, the influence on the existing manufacturing process is very small, and the prepared Na4Fe3(PO4)2P2O7the/C has high purity, good crystallinity and high ionic and electronic conductivity, and is suitable for large-scale production and application.
Drawings
Fig. 1 is an XRD pattern of the positive electrode material for sodium ion batteries prepared in comparative example 1 and examples 1 to 3, in which (a) is an original figure and (b) is a partially enlarged view of (a).
Fig. 2 is a charge-discharge curve diagram of assembled batteries of the positive electrode materials of the sodium-ion batteries prepared in comparative example 1 and examples 1 to 3.
Fig. 3 is a graph showing the impedance of the assembled battery of the positive electrode material for the sodium-ion battery prepared in comparative example 1 and examples 1 to 3.
Fig. 4 is a graph showing rate performance of assembled batteries of positive electrode materials of sodium ion batteries prepared in comparative example 1 and examples 1 to 3.
Detailed Description
In order that the invention may be more readily understood, specific embodiments thereof will be described further below.
Comparative example 1
Na free of iron defects4Fe3(PO4)2P2O7Synthesis and Performance testing of/C
Dissolving sodium dihydrogen phosphate, ferric nitrate nonahydrate and citric acid monohydrate in deionized water according to a molar ratio of 4:3:4, and continuously stirring at room temperature to obtain a light yellow-green solution. And (3) spray-drying the solution, wherein the air inlet temperature is 200 ℃, and the air outlet temperature is 170 ℃ to obtain a powdery precursor. Finally, in Ar/H2(H2Content of (1): 10%) in an atmosphere, at a heating rate of 2 ℃ to 500 ℃, calcining for 10h to obtain Na4Fe3(PO4)2P2O7a/C electrode material.
When the phase and crystallinity of the material were analyzed by XRD, Na free from iron defects was found as shown in FIG. 1(a)4Fe3(PO4)2P2O7the/C crystallinity is poor. From the partially enlarged XRD pattern 1(b), Na having no iron defect4Fe3(PO4)2P2O7The XRD diffraction pattern of the/C material contains characteristic diffraction peaks of sodium ferric phosphate and contains about 5 percent of sodium ferric phosphate impurities.
Weighing Na according to the mass ratio of 70:20:104Fe3(PO4)2P2O7Mixing the/C, the acetylene black and the PVDF, coating the mixture on an aluminum foil with the diameter of 19mm, and then drying the aluminum foil in vacuum at 120 ℃ for 12 hours to obtain the positive plate. Using metal sodium as counter electrode, 1mol/L NaClO4Ethylene carbonate/diethyl carbonate (volume ratio 1:1) is used as electrolyte, a diaphragm is cellgard2035, and the battery is assembled into a button battery in a glove box, wherein the model of the battery is CR 2016.
The test of constant current charging and discharging is carried out, and the current density is 26 mA/g. As shown in FIG. 2, the reversible specific capacity was 96.5mAh/g in the voltage range of 1.7-4.3V. The impedance test is carried out on the battery after charging and discharging,as a result, as shown in FIG. 3, Na having no iron defect was found4Fe3(PO4)2P2O7The interfacial charge transfer resistance of the/C electrode was 1250 ohms, indicating a lower material electronic as well as ionic conductivity.
Example 1
Providing Na containing iron defects4Fe2.97(PO4)2P2O7The preparation method of the/C sodium ion positive electrode material comprises the following steps:
dissolving sodium dihydrogen phosphate, ferric nitrate nonahydrate and citric acid monohydrate in deionized water according to a molar ratio of 4:2.97:4, and continuously stirring at room temperature to obtain a light yellow-green solution. And (3) spray-drying the solution, wherein the air inlet temperature is 200 ℃, and the air outlet temperature is 170 ℃ to obtain a powdery precursor. Finally, in Ar/H2(H2Content of (1): 10%) in an atmosphere, heating to 500 ℃ at a heating rate of 2 ℃, and calcining for 10 hours to obtain Na with iron defects4Fe2.97(PO4)2P2O7a/C electrode material.
When the phase and crystallinity of the material were analyzed by XRD, as shown in FIG. 1(a), Na free from iron defects as in comparative example 1 was found4Fe3(PO4)2P2O71% iron deficient Na/C4Fe2.97(PO4)2P2O7The crystallinity of the/C is greatly improved. From the partially enlarged XRD pattern 1(b), Na is shown4Fe2.97(PO4)2P2O7The impurity of ferric sodium phosphate in the/C material is reduced to 1 percent, which shows that the reduction of the iron content is beneficial to inhibiting the generation of the impurity of ferric sodium phosphate.
Weighing the prepared Na according to the mass ratio of 70:20:104Fe2.97(PO4)2P2O7Mixing the/C, the acetylene black and the PVDF, coating the mixture on an aluminum foil with the diameter of 19mm, and then drying the aluminum foil in vacuum at 120 ℃ for 12 hours to obtain the positive plate. Using metal sodium as counter electrode, 1mol/L NaClO4Ethylene carbonate/diethyl carbonate (volume ratio 1:1) as electrolyte, cellgard2035 as diaphragm, in glove boxThe button cell is assembled, and the model of the cell is CR 2016.
The test of constant current charging and discharging is carried out, and the current density is 26 mA/g. As shown in FIG. 2, the reversible specific capacity was 100.5mAh/g in the voltage range of 1.7-4.3V, and the test result was compared with Na having no iron defect in comparative example 14Fe3(PO4)2P2O7Compared with the comparative example C, the discharge capacity is improved by 5.0 mAh/g. FIG. 3 is a graph of the impedance after cycling versus Na without iron defects in comparative example 14Fe3(PO4)2P2O7The interface charge transfer resistance of the 1% iron-deficient material was reduced to 750 ohms compared to C, indicating that the presence of iron defects increased the electronic and ionic conductivity of the material, resulting in an increase in its capacity. FIG. 4 is a graph showing the rate performance of Na having no iron defect in comparative example 14Fe3(PO4)2P2O7Compared with C, the rate capability of the material with 1 percent of iron defects is better than that of the material without iron defects.
Example 2
Providing Na containing iron defects4Fe2.91(PO4)2P2O7The preparation method of the/C sodium ion positive electrode material comprises the following steps:
dissolving sodium dihydrogen phosphate, ferric nitrate nonahydrate and citric acid monohydrate in deionized water according to the molar ratio of 4:2.91:4, and continuously stirring at room temperature to obtain a light yellow-green solution. And (3) spray-drying the solution, wherein the air inlet temperature is 200 ℃, and the air outlet temperature is 170 ℃ to obtain a powdery precursor. Finally, in Ar/H2(H2Content of (1): 10%) in an atmosphere, heating to 500 ℃ at a heating rate of 2 ℃, and calcining for 10 hours to obtain Na with iron defects4Fe2.91(PO4)2P2O7a/C electrode material.
The phase and crystallinity of the material were analyzed by XRD, and Na having no iron defect was found as shown in FIG. 1(b)4Fe3(PO4)2P2O7Na with 3% iron deficiency compared with C4Fe2.91(PO4)2P2O7The crystallinity of the/C is further improved, and no sodium iron phosphate diffraction peak is found in an XRD diffraction spectrum, which indicates that the material does not contain sodium iron phosphate impurities.
Weighing the prepared Na according to the mass ratio of 70:20:104Fe2.91(PO4)2P2O7Mixing the/C, the acetylene black and the PVDF, coating the mixture on an aluminum foil with the diameter of 19mm, and then drying the aluminum foil in vacuum at 120 ℃ for 12 hours to obtain the positive plate. Using metal sodium as counter electrode, 1mol/L NaClO4Ethylene carbonate/diethyl carbonate (volume ratio 1:1) is used as electrolyte, a diaphragm is cellgard2035, and the battery is assembled into a button battery in a glove box, wherein the model of the battery is CR 2016.
The test of constant current charging and discharging is carried out, and the current density is 26 mA/g. As shown in FIG. 2, the reversible specific capacity was 110mAh/g in the voltage range of 1.7-4.3V, compared with Na having no iron defect in comparative example 14Fe3(PO4)2P2O7Compared with the comparative example C, the discharge capacity is improved by 13.5 mAh/g. FIG. 3 is a graph of the impedance after cycling versus Na without iron defects in comparative example 14Fe3(PO4)2P2O7The interfacial charge transfer resistance of the 3% iron-deficient material was reduced to 450 ohms compared to C. FIG. 4 is a graph showing the rate performance of Na having no iron defect in comparative example 14Fe3(PO4)2P2O7Compared with C, the rate capacity of the material with 3 percent of iron defects is obviously higher than that of the material without the iron defects, and the further increase of the content of the iron defects can improve the ionic and electronic conductivity of the material, thereby increasing the rate performance of the material.
Example 3
Providing Na containing iron defects4Fe2.85(PO4)2P2O7The preparation method of the/C sodium ion positive electrode material comprises the following steps:
dissolving sodium dihydrogen phosphate, ferric nitrate nonahydrate and citric acid monohydrate in deionized water according to a molar ratio of 4:2.85:4, and continuously stirring at room temperature to obtain a light yellow-green solution. Spray drying the above solution, and heatingThe temperature is 200 ℃, the air outlet temperature is 170 ℃, and the powdery precursor is obtained. Finally, in Ar/H2(H2Content of (1): 10%) in an atmosphere, heating to 500 ℃ at a heating rate of 2 ℃, and calcining for 10 hours to obtain Na with iron defects4Fe2.85(PO4)2P2O7a/C electrode material.
The phase and crystallinity of the material were analyzed by XRD, and Na having no iron defect was found as shown in FIG. 1(b)4Fe3(PO4)2P2O7Na with 5% iron deficiency compared with C4Fe2.85(PO4)2P2O7No sodium iron phosphate diffraction peak is contained in the/C, which indicates that iron defects are favorable for the generation of pure phase.
Weighing the prepared Na according to the mass ratio of 70:20:104Fe2.85(PO4)2P2O7Mixing the/C, the acetylene black and the PVDF, coating the mixture on an aluminum foil with the diameter of 19mm, and then drying the aluminum foil in vacuum at 120 ℃ for 12 hours to obtain the positive plate. Using metal sodium as counter electrode, 1mol/L NaClO4Ethylene carbonate/diethyl carbonate (volume ratio 1:1) is used as electrolyte, a diaphragm is cellgard2035, and the battery is assembled into a button battery in a glove box, wherein the model of the battery is CR 2016.
The test of constant current charging and discharging is carried out, and the current density is 26 mA/g. As shown in FIG. 2, the reversible specific capacity was 108mAh/g in the voltage range of 1.7-4.3V, compared with Na having no iron defect in comparative example 14Fe3(PO4)2P2O7Compared with the comparative example C, the discharge capacity is improved by 11.5 mAh/g. FIG. 3 is a graph of the impedance after cycling versus Na without iron defects in comparative example 14Fe3(PO4)2P2O7The interfacial charge transfer resistance of the 1% iron-deficient material was reduced to 550 ohms compared to C. FIG. 4 is a graph showing the rate performance of Na having no iron defect in comparative example 14Fe3(PO4)2P2O7Compared with C, the rate capability of the material with 5 percent of iron defects is better than that of the material without iron defects.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. Na4Fe3-x(PO4)2P2O7The positive electrode material of the sodium-ion battery is characterized by being Na4Fe3-x(PO4)2P2O7And C, wherein Na4Fe3-x(PO4)2P2O7Middle, 0<x<0.5, iron defects were present.
2. The positive electrode material for sodium-ion batteries according to claim 1, characterized in that Na4Fe3-x(PO4)2P2O7The mass ratio of C to C is 9.5:0.5-9.9: 0.1.
3. The sodium-ion battery positive electrode material according to claim 1, wherein 0.05< x < 0.15.
4. The sodium-ion battery positive electrode material as claimed in claim 1, which is prepared by mixing and calcining raw materials of a sodium source compound, an iron source compound, a phosphorus source compound, a carbon source compound and a reducing agent, wherein the molar ratio of sodium to iron in the raw materials is controlled to be 4: (3-x), 0< x < 0.5.
5. Na according to any one of claims 1 to 44Fe3-x(PO4)2P2O7The preparation method of the positive electrode material of the/C sodium-ion battery is characterized by comprising the following steps of:
(1) uniformly mixing raw materials of a sodium source compound, an iron source compound, a phosphorus source compound, a carbon source compound and a reducing agent, and fully drying to obtain a mixed raw material, wherein the molar ratio of sodium to iron in the mixed raw material is 4: (3-x), 0< x < 0.5;
(2) placing the mixed raw material in the step (1) in an inert atmosphere or a reducing atmosphere, and preserving the heat for 4-20 hours at the temperature of 350-4Fe3-x(PO4)2P2O7the/C sodium ion battery positive electrode material.
6. The production method according to claim 5, wherein in the step (1), the molar ratio of sodium and phosphorus elements is 1:1, the molar ratio of the carbon source compound and the iron source compound is (0.1-5):1, and the molar ratio of the reducing agent and the iron source compound is (0.1-5): 1.
7. The production method according to claim 5,
the iron source compound is one or more of iron powder, ferric citrate, ferrous citrate, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, ferric chloride, ferrous chloride, ferroferric oxide, ferric oxide, ferrous oxide, ferric oxalate, ferrous oxalate, ferric acetate, ferric phosphate, ferric pyrophosphate and ferrous ammonium sulfate;
the phosphorus source compound is one or more of sodium dihydrogen phosphate, sodium monohydrogen phosphate, phosphoric acid, ammonium dihydrogen phosphate, triammonium phosphate, pyrophosphoric acid, sodium pyrophosphate and sodium dihydrogen pyrophosphate;
the sodium source compound is one or more of sodium dihydrogen phosphate, sodium carbonate, sodium nitrate, sodium oxalate, sodium acetate, sodium sulfate, sodium hydroxide, sodium formate, sodium citrate, sodium pyrophosphate and sodium dihydrogen pyrophosphate.
8. The production method according to claim 5,
the reducing agent is one or more of oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butyraldehyde, lactic acid, citric acid, malic acid, oxalic acid, adipic acid, citric acid, soluble starch, ascorbic acid, sucrose and glucose;
the carbon source compound is one or more of oxalic acid, ascorbic acid, formaldehyde, acetaldehyde, n-butyl aldehyde, lactic acid, citric acid, malic acid, oxalic acid, adipic acid, citric acid, soluble starch, ascorbic acid, sucrose and glucose.
9. The preparation method according to claim 5, wherein in the step (1), the raw materials are mixed uniformly by one or two of ball milling and aqueous solution dissolution; the drying method of the mixture raw material comprises one or more of forced air drying, vacuum drying, freeze drying and spray drying; in the step (2), the inert atmosphere is nitrogen or argon; the reducing atmosphere is nitrogen-hydrogen mixed gas or argon-hydrogen mixed gas.
10. Na according to any one of claims 1 to 44Fe3-x(PO4)2P2O7The application of the/C sodium ion battery positive electrode material in the sodium ion battery.
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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113328073A (en) * 2021-05-24 2021-08-31 上海电力大学 Modified iron-based polyanion compound cathode material and preparation method thereof
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CN116845236A (en) * 2023-09-01 2023-10-03 北京禾电科技有限责任公司 Polyanionic sodium ion battery positive electrode material, preparation method and application
WO2024111514A1 (en) * 2022-11-22 2024-05-30 日本電気硝子株式会社 Positive electrode mixture for all-solid-state sodium ion secondary battery, positive electrode for all-solid-state sodium ion secondary battery, and all-solid-state sodium ion secondary battery

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2007202605A1 (en) * 2001-12-21 2007-06-28 Massachusetts Institute Of Technology Conductive lithium storage electrode
CN106340650A (en) * 2016-11-09 2017-01-18 中南大学 Preparation method of ferric pyrophosphate and application of ferric pyrophosphate in sodium-ion batteries
CN106575752A (en) * 2014-08-05 2017-04-19 3M创新有限公司 Cathode compositions for lithium-ion batteries
CN107017395A (en) * 2017-05-22 2017-08-04 中南大学 A kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application
CN108046231A (en) * 2017-11-13 2018-05-18 中南大学 A kind of sodium-ion battery positive material and preparation method thereof
CN108292759A (en) * 2015-09-14 2018-07-17 纳米技术仪器公司 Alkali metal with high volume energy density and gravimetric energy density or basic ion battery
WO2018133339A1 (en) * 2017-01-17 2018-07-26 东莞市迈科科技有限公司 Polyanion-type sodium ion battery positive electrode material and preparation method therefor
CN108511704A (en) * 2018-03-06 2018-09-07 上海应用技术大学 A kind of magnesium substitution vanadium phosphate sodium/carbon composite anode material of sodium-ion battery and preparation method thereof
CN108565418A (en) * 2018-04-03 2018-09-21 武汉大学 A kind of novel sodium-ion battery positive material and preparation method thereof
CN109616648A (en) * 2018-12-10 2019-04-12 中国科学院物理研究所 A kind of secondary battery electrode material and battery containing intrinsic vacancy
CN110226252A (en) * 2018-07-27 2019-09-10 辽宁星空钠电电池有限公司 A kind of polyanionic sodium-ion battery positive material and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2007202605A1 (en) * 2001-12-21 2007-06-28 Massachusetts Institute Of Technology Conductive lithium storage electrode
CN106575752A (en) * 2014-08-05 2017-04-19 3M创新有限公司 Cathode compositions for lithium-ion batteries
CN108292759A (en) * 2015-09-14 2018-07-17 纳米技术仪器公司 Alkali metal with high volume energy density and gravimetric energy density or basic ion battery
CN106340650A (en) * 2016-11-09 2017-01-18 中南大学 Preparation method of ferric pyrophosphate and application of ferric pyrophosphate in sodium-ion batteries
WO2018133339A1 (en) * 2017-01-17 2018-07-26 东莞市迈科科技有限公司 Polyanion-type sodium ion battery positive electrode material and preparation method therefor
CN107017395A (en) * 2017-05-22 2017-08-04 中南大学 A kind of carbon coating manganese pyrophosphate sodium@graphene oxide composite materials with sandwich structure and its preparation method and application
CN108046231A (en) * 2017-11-13 2018-05-18 中南大学 A kind of sodium-ion battery positive material and preparation method thereof
CN108511704A (en) * 2018-03-06 2018-09-07 上海应用技术大学 A kind of magnesium substitution vanadium phosphate sodium/carbon composite anode material of sodium-ion battery and preparation method thereof
CN108565418A (en) * 2018-04-03 2018-09-21 武汉大学 A kind of novel sodium-ion battery positive material and preparation method thereof
CN110226252A (en) * 2018-07-27 2019-09-10 辽宁星空钠电电池有限公司 A kind of polyanionic sodium-ion battery positive material and preparation method thereof
CN109616648A (en) * 2018-12-10 2019-04-12 中国科学院物理研究所 A kind of secondary battery electrode material and battery containing intrinsic vacancy

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* Cited by examiner, † Cited by third party
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CN114068938A (en) * 2022-01-17 2022-02-18 中南大学 Sodium vanadium fluorophosphate coated sodium iron pyrophosphate phosphate composite material and preparation method and application thereof
CN114068938B (en) * 2022-01-17 2022-04-15 中南大学 Sodium vanadium fluorophosphate coated sodium iron pyrophosphate phosphate composite material and preparation method and application thereof
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
CN114538403B (en) * 2022-01-27 2023-08-22 廖小珍 Preparation method and application of sodium ion battery anode material sodium ferric pyrophosphate phosphate
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CN115535990A (en) * 2022-09-28 2022-12-30 华中科技大学 Liquid phase preparation of Na from iron oxide red 4 Fe 3 (PO 4 ) 2 P 2 O 7 Method and use of/C
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