CN113060714B - Slave FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) Method (2) - Google Patents

Slave FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) Method (2) Download PDF

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CN113060714B
CN113060714B CN202110207075.7A CN202110207075A CN113060714B CN 113060714 B CN113060714 B CN 113060714B CN 202110207075 A CN202110207075 A CN 202110207075A CN 113060714 B CN113060714 B CN 113060714B
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sodium
fepo
pyrophosphate
slave
liquid phase
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CN113060714A (en
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曹余良
陈重学
付承龙
赵阿龙
熊健
王勤
陈世涛
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Hubei Wanrun New Energy Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a secondary FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) Method of (1), Na4Fe3(PO4)2(P2O7) The preparation method comprises the following steps: mixing iron phosphate, a carbon source, a sodium source and a phosphorus source in water according to a certain stoichiometric ratio; sanding for 3-12 h to control the grain diameter between 1-0.1 μm; spray drying to obtain a precursor, sintering the precursor powder in an inert atmosphere at the sintering temperature of 400-600 ℃ for 4-15 h to obtain Na4Fe3(PO4)2(P2O7) And (3) powder. The method provided by the invention adopts FePO4In situ synthesis of Na as a growth template4Fe3(PO4)2(P2O7) The spherical powder has controllable product particle size, green and simple process and easy amplification. Na produced in the present invention4Fe3(PO4)2(P2O7) The lithium ion battery anode has the advantages of low cost and stable structure, and has excellent cycle performance when being applied to a sodium ion battery anode.

Description

Slave FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) Method (2)
Technical Field
The invention belongs to the technical field of preparation of battery electrode material powder, and particularly relates to FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (1).
Background
The lithium ion battery, as a representative secondary battery with the most excellent comprehensive performance at present, dominates the markets of portable electronic products and electric automobiles, and gradually expands the energy storage field. However, the reserve of lithium resources in the earth's crust is limited and about 73% is concentrated in a few countries in south america. It is estimated that the base reserve of globally exploitable lithium resources is about 25M tons. The current global electric automobile holding amount exceeds 500 thousands, 8000 thousands of automobiles are expected to be broken through in 2030 year, and the consumption increment of lithium resources is undoubtedly huge in the future. Meanwhile, the scale of the energy storage market is in a growing situation. Therefore, the shortage of lithium resources makes it difficult for the lithium ion battery to support both electric vehicles and large-scale energy storage industries. In order to break through the brake which is scarce in war resources, the development of a next generation of novel energy storage battery which is more advantageous in resources and cost is imperative.
The sodium metal element is abundant in the earth crust, the distribution area is wide, the physical and chemical properties of sodium and lithium are very similar, the electrode potential is relatively close, and the sodium ion battery constructed based on the deintercalation mechanism has more advantages in resources and cost compared with the lithium ion battery in the application field of large-scale energy storage with low requirement on energy density. However, the development of sodium ion batteries is currently restricted by the positive electrode materials. The positive electrode materials currently under study include oxides, prussian blue and polyanions, and the polyanion type positive electrode material is undoubtedly the best choice compared with the other two. Wherein, Na4Fe3(PO4)2(P2O7) Has received a great deal of attention in view of its good structural stability and environmental friendliness. However, Na4Fe3(PO4)2(P2O7) The electronic and ionic conductivity of (2) is low, and nanocrystallization and carbon coating modification are required. Preparation of Na by traditional synthetic method4Fe3(PO4)2(P2O7) The micro-nano powder is easy to agglomerate, so that the specific surface area of the powder and the utilization rate of electrode materials are not high. For increasing Na4Fe3(PO4)2(P2O7) The researchers have adopted different synthesis methods, such as compounding with graphene, template method and the like to obtain Na4Fe3(PO4)2(P2O7) Micro-nano powder. However, these methods are technically complexIs trivial, has high cost and is not easy to be scaled up. Therefore, a novel simple and easily-amplified Na is developed4Fe3(PO4)2(P2O7) The preparation method of (A) is imminent.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a slave FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method comprises the following steps:
(1) respectively weighing FePO according to stoichiometric ratio4A sodium source, a phosphorus source and a carbon source are uniformly dispersed in deionized water;
(2) putting the dispersion liquid into a sand mill, adding a sand grinding medium, and performing wet-method sand grinding for 3-12 h, wherein the particle size is controlled to be 1-0.1 mu m;
(3) transferring the sanded reaction liquid into a spray dryer for spray granulation;
(4) sintering the sprayed powder in an inert atmosphere at the sintering temperature of 400-650 ℃ for 4-15 h to obtain the Na4Fe3(PO4)2(P2O7) And (3) powder.
Preferably, the sodium source in step (1) comprises one or more of inorganic sodium salt, organic sodium salt, metallic sodium and sodium oxide.
Further preferably, the inorganic sodium salt includes at least one of trisodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate, monosodium monohydrogen pyrophosphate, sodium carbonate, and sodium bicarbonate.
Further preferably, the organic sodium salt comprises at least one of sodium acetate, sodium oxalate and sodium citrate; the sodium oxide comprises at least one of sodium oxide and sodium peroxide.
Preferably, the phosphorus source of step (1) comprises one or more of phosphoric acid, a phosphate and a pyrophosphate.
Further preferably, the phosphate comprises at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate; the pyrophosphate comprises at least one of sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate and monosodium trihydrogen pyrophosphate.
Preferably, the carbon source in step (1) includes one or more of graphite, carbon black, carbon nanotube, graphene, and one or more of common organic carbonaceous materials including citric acid, glucose, sucrose, and the like.
Preferably, the sanding manner of the sand mill in the step (2) includes one of a disc type, a pin-and-rod type and a turbine type.
Preferably, the sanding medium in step (2) comprises one or more of natural sand, glass beads, steel beads, zirconia beads, zirconium silicate beads and agate beads.
Preferably, the sintering atmosphere in step (4) includes one of argon, nitrogen, argon-hydrogen gas mixture, and nitrogen-hydrogen gas mixture.
Preferably, the sintering temperature zone in step (4) includes all temperatures in 400-650 ℃ and various temperature rising and reducing gradients.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following advantages:
1. with FePO4In situ synthesis of Na as a growth template4Fe3(PO4)2(P2O7) The particle size of the product is controllable;
2. the used raw materials comprise iron phosphate, a sodium source, a phosphorus source and a carbon source which are cheap and easily obtained, the distribution is wide, the preparation process is green and simple, the amplification is easy, and the raw materials can be Na4Fe3(PO4)2(P2O7) Provides an alternative route to pilot plant production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 shows a positive electrode active material Na prepared in example 1 of the present invention4Fe3(PO4)2(P2O7) Scanning electron microscopy of (a).
FIG. 2 shows a positive electrode active material Na prepared in example 1 of the present invention4Fe3(PO4)2(P2O7) XRD pattern of (a).
Fig. 3 is a charge-discharge curve diagram of the sodium ion battery prepared in example 1 of the present invention.
Fig. 4 is a charge-discharge curve diagram of the sodium ion battery prepared in example 2 of the present invention.
Fig. 5 is a charge-discharge curve diagram of the sodium ion battery prepared in example 3 of the present invention.
Fig. 6 is a graph of the cycling profile at 10C current density for the sodium ion battery prepared in example 1 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A positive electrode active material with chemical formula of Na4Fe3(PO4)2(P2O7) The preparation method of the positive active material comprises the following steps:
with sodium pyrophosphate Na4P2O7、FePO4Sodium acetate CH3COONa and citric acid are used as raw materials; wherein, sodium pyrophosphate Na4P2O7Is both a sodium source and a phosphorus source, FePO4Is iron source, sodium acetate CH3COONa is used as a sodium supplement source, and citric acid is used as a carbon source;
4.4605 g of Na4P2O7·10 H2O、9.06 g FePO43.2808g of sodium acetate and 8.4056g of citric acid monohydrate are added into 500mL of water, ball milled for 3h at the rotating speed of 20rpm, then sanded for 3h at 2000rpm, and then fed at 80% of air inlet speed, 130 ℃ of air inlet temperature and 0.5% of feeding speed for spray drying to obtain a precursor; then putting the precursor in argon atmosphere, and calcining at 550 ℃ for 10 h to obtain Na4Fe3(PO4)2(P2O7). And assembling the button cell in a glove box with water oxygen below 0.01 ppm.
FIG. 1 shows a positive electrode active material Na prepared in this example4Fe3(PO4)2(P2O7) The scanning electron microscope picture of (2) shows that the powder is in a similar spherical shape and the particle size of the product is controllable. FIG. 2 shows a positive electrode active material Na prepared in this example4Fe3(PO4)2(P2O7) XRD pattern of (a). As can be seen from FIG. 3, the reversible capacity of the button half cell assembled by the material prepared in the embodiment as the positive electrode material reaches 105mAh/g at 0.2C. As can be seen from FIG. 6, the reversible capacity of the assembled button half cell reaches 66mAh/g at 10C, and the capacity retention rate after 5000 cycles is more than 83.5%.
Example 2
A positive electrode active material with chemical formula of Na4Fe3(PO4)2(P2O7) The preparation method of the positive active material comprises the following steps:
with NaH2PO4、FePO4Citric acid is used as a raw material; wherein, NaH2PO4Is both a sodium source and a phosphorus source, FePO4Is an iron source, and sucrose is a carbon source;
18.7212 g NaH2PO4、7.185g FePO412.6084 g of citric acid monohydrate was dispersed in 500mL of water, ball milled at 20rpm for 3h, then sanded at 2000rpm for 3h, and then milled at 8Feeding at an air inlet rate of 0%, an air inlet temperature of 130 ℃ and a feeding rate of 0.5%, and performing spray drying to obtain a precursor;
then placing the precursor in argon atmosphere, and calcining for 5 hours at the temperature of 600 ℃ to obtain Na4Fe3(PO4)2(P2O7). And assembling the button cell in a glove box with water oxygen below 0.01 ppm. As can be seen from FIG. 4, Na prepared in this example4Fe3(PO4)2(P2O7) The reversible capacity of the button half cell assembled as the positive active material reaches 74mAh/g at 0.2C.
Example 3
A positive electrode active material with chemical formula of Na4Fe3(PO4)2(P2O7) The preparation method of the positive active material comprises the following steps:
with sodium pyrophosphate Na4P2O7、FePO4、Na2CO3Glucose is used as a raw material; wherein, sodium pyrophosphate Na4P2O7Is both a sodium source and a phosphorus source, FePO4Is a source of iron, Na2CO3For supplementing a sodium source, citric acid is used as a carbon source;
8.921 g of Na4P2O7·10 H2O、18.12 g FePO4、6.5616g Na2CO316.8112 adding glucose into 500mL of absolute ethyl alcohol, ball-milling at a rotating speed of 20rpm for 3h, sanding at 2000rpm for 3h, feeding at an air inlet speed of 80%, an air inlet temperature of 130 ℃ and a feeding speed of 0.5%, and spray-drying to obtain a precursor;
then putting the precursor in argon atmosphere, calcining for 15h at the temperature of 400 ℃ to obtain Na4Fe3(PO4)2(P2O7). And assembling the button cell in a glove box with water oxygen below 0.01 ppm.
As can be seen from FIG. 5, Na prepared in this example4Fe3(PO4)2(P2O7) Button half cell assembled as positive active materialThe reversible capacity reaches 76mAh/g at 0.2 ℃.

Claims (8)

1. Slave FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method is characterized by comprising the following steps:
(1) respectively weighing FePO according to stoichiometric ratio4A sodium source, a phosphorus source and a carbon source are uniformly dispersed in deionized water; FePO in the step (1)4The particle size of (A) is 0.1-10 μm;
(2) ball-milling the dispersion liquid for 3h at the rotating speed of 20rpm, then placing the dispersion liquid into a sand mill, adding a sand milling medium, and carrying out wet grinding for 3h at the rotating speed of 2000rpm, wherein the particle size is controlled to be 1-0.1 mu m;
(3) transferring the sanded reaction liquid into a spray dryer for spray granulation;
(4) sintering the sprayed powder in an inert atmosphere at the sintering temperature of 400-650 ℃ for 4-15 h to obtain the Na4Fe3(PO4)2(P2O7) And (3) powder.
2. A slave FePO according to claim 14Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (2), wherein the sodium source used in step (1) comprises one or more of inorganic sodium salt, organic sodium salt, metallic sodium, and sodium oxide; the inorganic sodium salt comprises at least one of trisodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate, monosodium dihydrogen pyrophosphate, sodium carbonate and sodium bicarbonate; the organic sodium salt comprises at least one of sodium acetate, sodium oxalate and sodium citrate; the sodium oxide comprises at least one of sodium oxide and sodium peroxide.
3. A slave FePO according to claim 14Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (1), characterized in thatThe phosphorus source used in the step (1) comprises one or more of phosphoric acid, phosphate and pyrophosphate; the phosphate comprises at least one of sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the pyrophosphate comprises at least one of sodium pyrophosphate, trisodium monohydrogen pyrophosphate, disodium dihydrogen pyrophosphate and monosodium trihydrogen pyrophosphate.
4. A slave FePO according to claim 14Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (2), wherein the carbon source used in step (1) comprises one or more of graphite, activated carbon, carbon nanotubes and graphene, and comprises one or more of citric acid, glucose and sucrose.
5. A slave FePO according to claim 14Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (2), wherein the sanding manner of the sander in the step (2) comprises one of a disc type, a pin-and-rod type and a turbine type.
6. A slave FePO according to claim 14Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (2), wherein the sanding medium in step (2) comprises one or more of natural sand, glass beads, steel beads, zirconia beads, zirconium silicate beads, and agate beads.
7. A slave FePO according to claim 14Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method of (4), wherein the sintering atmosphere in step (4) comprises one of argon, nitrogen, argon-hydrogen gas mixture, and nitrogen-hydrogen gas mixture.
8. A slave as claimed in claim 1FePO4Liquid phase preparation of Na4Fe3(PO4)2(P2O7) The method is characterized in that the sintering temperature zone in the step (4) comprises all temperatures of 400-650 ℃ and various temperature rising and reducing gradients.
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