CN114906832A - Preparation method of sodium iron fluorophosphate cathode material - Google Patents
Preparation method of sodium iron fluorophosphate cathode material Download PDFInfo
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- CN114906832A CN114906832A CN202210242465.2A CN202210242465A CN114906832A CN 114906832 A CN114906832 A CN 114906832A CN 202210242465 A CN202210242465 A CN 202210242465A CN 114906832 A CN114906832 A CN 114906832A
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- cathode material
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- iron fluorophosphate
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- HIDOPYNXWKECHK-UHFFFAOYSA-L P(=O)([O-])([O-])F.[Fe+2].[Na+] Chemical compound P(=O)([O-])([O-])F.[Fe+2].[Na+] HIDOPYNXWKECHK-UHFFFAOYSA-L 0.000 title claims abstract description 21
- 239000010406 cathode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- -1 titanates Chemical class 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000013024 sodium fluoride Nutrition 0.000 claims description 6
- 239000011775 sodium fluoride Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920000447 polyanionic polymer Polymers 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- 150000001642 boronic acid derivatives Chemical class 0.000 abstract description 2
- 150000004760 silicates Chemical class 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 229910004591 Na2FePO4F Inorganic materials 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- IYHPPEDNKYRLNK-UHFFFAOYSA-K lithium;hydrogen phosphate;iron(2+);fluoride Chemical compound [Li+].[F-].[Fe+2].OP([O-])([O-])=O IYHPPEDNKYRLNK-UHFFFAOYSA-K 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention discloses a preparation method of a sodium iron fluorophosphate cathode material, which takes a sodium ion battery material precursor as a raw material, adopts a solid-phase synthesis method, carries out heat treatment under the protection of inert atmosphere to ensure that glucose forms a carbon layer which can be attached to the surface of the precursor, and calcines the heat-treated material to obtain the sodium iron fluorophosphate/carbon composite material for a sodium ion battery Synthesis of silicates, titanates, borates, sulfates and other polyanionic sodium ion secondary battery carbon-coated positive electrode materials.
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a preparation method of a sodium iron fluorophosphate cathode material.
Background
The resource and environment problems are increasingly becoming the first problems of human survival and continuous development, in the face of increasingly intensified global warming, all countries in the world have a global conference on the problem of carbon emission for many times, and all countries are continuously performing carbon emission reduction, on one hand, because petroleum is a polluting resource, a large amount of pollution emission is caused by using all countries in the world for hundreds of years, especially, the emission of gases such as carbon dioxide causes great pollution to the global environment, and the problems of global warming and the like are also indirectly caused, therefore, all countries in the world continuously seek the alternative resources of petroleum products to continuously reduce the dependence and use on petroleum consumption; on the other hand, scientists all over the world are continuously searching for new energy sources to replace or partially replace petroleum energy sources, such as hydrogen energy sources, fuel cells, new lithium ion batteries, new sodium ion batteries and the like, and the new energy source solution is provided.
Since the 21 st century, a novel lithium ion battery is rapidly developed and plays a good role in the fields of electronic consumer goods, automobile markets, energy storage markets, military products and the like, the high-performance lithium ion battery has the obvious advantages of high energy density, high weight density, good charge-discharge cycle performance, no memory effect and the like, but with continuous and rapid consumption of global lithium resources, the prices of lithium ores and the like continuously rise, the price of high lithium ores at the upstream rises continuously, the price of a terminal battery continuously rises, meanwhile, the global lithium ore resources are mainly mastered in several countries such as Australia and Chile, if the import and export markets are unstable, the price of the domestic lithium battery is unstable, and more serious lithium shortage can cause social problems.
Therefore, the appearance of the novel sodium ion battery is helpful for solving the problems of raw materials and price of the lithium ion battery, and can play a very important strategic resource role in stabilizing the contradiction between the battery market and the social supply and demand, the sodium ion battery has functions similar to those of the lithium ion battery, such as high energy density, high weight density, good charge-discharge cycle performance, no memory effect and other obvious advantages, and also has the characteristics of abundant national reserves of the raw material sodium, easy preparation, low price and the like, but the sodium ion battery has similar defects with the lithium ion battery: the cycling stability and the structural stability are generally poor. Therefore, a preparation method of the sodium iron fluorophosphate cathode material is provided.
Disclosure of Invention
The invention aims to provide a preparation method of a sodium iron fluorophosphate cathode material, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a sodium iron fluorophosphate cathode material, wherein fluoride ions are added into the cathode material of a sodium ion battery, and the preparation method comprises the following steps: preparing a precursor for a sodium-ion battery positive electrode material, placing the precursor in a ball milling tank or a beaker to contact with glucose, and drying after ball milling; preparing a precursor for a sodium-ion battery positive electrode material, placing the precursor in a ball milling tank or a beaker to contact with glucose, and drying after ball milling; and step three, calcining the heat-treated material to obtain the sodium iron fluorophosphate/carbon composite material for the sodium ion battery.
Preferably, in the first step, the precursor uses a soluble compound containing ferrous ions as an iron source, and uses sodium fluoride as a sodium source and a fluoride ion source.
Preferably, the sodium fluoride is added in an amount.
Preferably, in the step one, the ball milling time is 6 to 8 hours.
Preferably, in the step one, the drying treatment is drying in a drying oven for 12 hours at 100 ℃.
Preferably, in the first step, the glucose is added in an amount.
Preferably, in the second step, the heat treatment is performed at a constant temperature of 300-400 ℃ for 3 hours.
Preferably, in the third step, the calcination is high temperature calcination at 600 ℃ for 8-12 hours.
Preferably, the synthesized positive electrode material comprises a phosphate system positive electrode material, a silicate positive electrode material, a titanate positive electrode material, a borate positive electrode material, a sulfate positive electrode material and other positive electrode materials for polyanion sodium-ion secondary batteries.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds fluorinion on the basis of the original ferric sodium phosphate, further increases the battery voltage of the battery material and the charging and discharging stability of the battery, adopts an energy-saving, low-carbon, environment-friendly and economic green synthetic route, has no environmental pollution and is easy to industrialize, the prepared lithium iron fluoride phosphate battery takes soluble compounds containing ferrous ions as an iron source and takes sodium fluoride as a sodium source and a fluorinion source, mixing glucose with the mass ratio of 5% in a high-temperature furnace, calcining at the high temperature of 600 ℃ for 8-12 hours, the obtained nano-grade sodium iron fluorophosphate with good crystallinity has stable performance, good cycle performance and high charging and discharging efficiency, and the cost is low, the raw materials are rich, and the method can be used for synthesizing carbon-coated cathode materials for phosphate systems, silicates, titanates, borates, sulfates and other polyanion sodium ion secondary batteries.
Drawings
FIG. 1 is an XRD pattern of a synthesized Na2FePO4F material;
FIG. 2 is an AC impedance plot of the synthesized Na2FePO4F material;
FIG. 3 is TEM image A of a synthesized Na2FePO4F material;
FIG. 4 is TEM image B of the synthesized Na2FePO4F material;
FIG. 5 is a charge and discharge graph of the synthesized Na2FePO4F material;
FIG. 6 is a graph of the cycle life of the synthesized Na2FePO4F material;
figure 7 is a cyclic voltammogram of the synthesized Na2FePO4F material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1-7, the present invention provides a technical solution: a preparation method of sodium iron fluorophosphate cathode material, which takes sodium ion battery material precursor as raw material and adopts a solid phase synthesis method to directly synthesize the cathode material for the sodium ion battery under the protection of inert atmosphere, comprises the following steps:
(1) 5mmol/0.8995g of ferrous oxalate was weighed into a ball mill jar.
(2) 5mmol/0.7801g of sodium dihydrogen phosphate are weighed into a ball mill pot.
(3) 5mmol/0.4201g of sodium fluoride was weighed into a ball mill pot.
(4) 0.3716g of glucose with the mass fraction of 5 percent is weighed and added into a ball milling tank.
(5) 30ml of absolute ethyl alcohol is weighed and added into a ball milling tank.
(6) The dispersed compound was ball milled for 6 hours.
(7) And (5) placing the ball-milled sample in a drying oven for 12 hours and drying at 100 ℃.
(8) The dried sample was ground and placed in a 5ml small crucible and calcined at 600 ℃ for 10 hours to obtain a black powder sample.
(9) The powder samples were ground and plated on double-sided aluminum foil using a 5 μm laminator.
(10) The sample was dried for 12 hours, and cut into pieces using a cutter, and the positive electrode material was cut into pieces having a diameter of 12 mm.
(11) And assembling the battery according to the sequence of the negative electrode shell, the counter electrode sodium sheet, the diaphragm, the electrolyte, the positive electrode material, the gasket, the elastic sheet and the positive electrode shell.
(12) The material Na2FePO4F is synthesized, and an XRD pattern is shown in figure 1; FIG. 2 is an AC impedance plot; FIGS. 3 and 4 are TEM images of a material; FIG. 5 is a charge-discharge graph of a material; FIG. 6 is a graph of the cycle life of a material; figure 7 is a cyclic voltammogram of the synthesized Na2FePO4F material.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. A preparation method of a sodium iron fluorophosphate cathode material is characterized in that fluoride ions are added into the cathode material of a sodium ion battery, and comprises the following steps:
preparing a precursor for a sodium-ion battery positive electrode material, placing the precursor in a ball milling tank or a beaker to contact with glucose, and drying after ball milling;
carrying out heat treatment on glucose loaded with the precursor for the sodium-ion battery anode material under the protection of inert gas, so that a glucose-formed carbon layer can be attached to the surface of the precursor;
and step three, calcining the heat-treated material to obtain the sodium iron fluorophosphate/carbon composite material for the sodium ion battery.
2. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: in the first step, the precursor takes soluble compounds containing ferrous ions as an iron source, and takes sodium fluoride as a sodium source and a fluoride ion source.
3. The method for preparing the sodium iron fluorophosphate cathode material according to claim 3, which is characterized in that: the amount of sodium fluoride added.
4. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: in the first step, the ball milling time is 6-8 hours.
5. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: in the first step, the drying treatment is drying for 12 hours at 100 ℃ in a drying oven.
6. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: in the first step, the addition amount of glucose is determined.
7. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: in the second step, the heat treatment is constant temperature within the range of 300-400 ℃ for 3 hours.
8. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: in the third step, the calcination is carried out for 8 to 12 hours at the high temperature of 600 ℃.
9. The method for preparing the sodium iron fluorophosphate cathode material according to claim 2, which is characterized in that: the synthesized positive electrode material comprises a phosphate system positive electrode material, a silicate positive electrode material, a titanate positive electrode material, a borate positive electrode material, a sulfate positive electrode material and other positive electrode materials for polyanion sodium-ion secondary batteries.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN102810669A (en) * | 2011-05-31 | 2012-12-05 | 现代自动车株式会社 | Positive electrode material for secondary battery and method for manufacturing the same |
| CN102306772A (en) * | 2011-08-17 | 2012-01-04 | 中南大学 | Method for preparing fluorine sodium ferrous phosphate positive electrode material of mixed ion battery |
| 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 |
| CN109659525A (en) * | 2018-12-12 | 2019-04-19 | 苏州大学 | A method of preparing manganese fluorophosphate ferrisodium composite positive pole |
| CN110931781A (en) * | 2019-10-14 | 2020-03-27 | 桂林理工大学 | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material |
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