CN112456464A - Method for preparing electrode material by using eutectic salt - Google Patents
Method for preparing electrode material by using eutectic salt Download PDFInfo
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- CN112456464A CN112456464A CN202011337215.4A CN202011337215A CN112456464A CN 112456464 A CN112456464 A CN 112456464A CN 202011337215 A CN202011337215 A CN 202011337215A CN 112456464 A CN112456464 A CN 112456464A
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- electrode material
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- eutectic salt
- choline chloride
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- 230000005496 eutectics Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000003839 salts Chemical class 0.000 title claims abstract description 26
- 239000007772 electrode material Substances 0.000 title claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 71
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 51
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 40
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 40
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 40
- 229960003178 choline chloride Drugs 0.000 claims abstract description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000005406 washing Methods 0.000 claims abstract description 26
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910001386 lithium phosphate Inorganic materials 0.000 claims abstract description 12
- 239000002608 ionic liquid Substances 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000000975 co-precipitation Methods 0.000 claims description 7
- 229940099596 manganese sulfate Drugs 0.000 claims description 5
- 235000007079 manganese sulphate Nutrition 0.000 claims description 5
- 239000011702 manganese sulphate Substances 0.000 claims description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 20
- 239000007774 positive electrode material Substances 0.000 description 10
- 239000012266 salt solution Substances 0.000 description 10
- 229910019142 PO4 Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000003517 fume Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000001570 ionothermal synthesis Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000374 eutectic mixture Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a method for preparing an electrode material by using eutectic salt, which comprises the following steps: 1) preparation of eutectic salt: selecting choline chloride as a hydrogen bond acceptor, selecting at least one of ethylene glycol, urea, oxalic acid and citric acid as a hydrogen bond donor, mixing the hydrogen bond acceptor and the hydrogen bond donor, stirring and standing to obtain eutectic ionic liquid; 2) preparing an electrode material: eutectic ionic liquid and Li3PO4Sequentially adding the powder and a manganese source into an application container, stirring, transferring into a hydrothermal kettle for hydrothermal reaction, centrifuging, removing upper-layer liquid, respectively performing centrifugal washing by using deionized water and ethanol, obtaining powder after washing, and drying the powder to obtain the lithium manganese phosphate. The method for preparing the lithium ion battery cathode material lithium manganese phosphate by using the eutectic salt as the template has the advantages of environmental protectionThe method has the advantages of simple process, and the prepared product has smaller charge transfer and ion diffusion resistance and shows excellent electrochemical performance.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to a method for preparing an electrode material by utilizing eutectic salt.
Background
The application of the lithium ion battery is very wide, wherein the anode material is the most important component of the lithium ion battery and is also the key for determining the performance of the lithium ion battery. The lithium manganese phosphate anode material has the advantages of rich raw material sources, low synthesis cost, high energy density, environmental friendliness and the like, so that the lithium manganese phosphate anode material has a great prospect and becomes the key point of current research. At present, the methods for preparing the lithium manganese phosphate have more ways, wherein the most common method is a solid-phase method, and the pure-phase lithium manganese phosphate can be prepared by adopting the solid-phase method, but the products prepared by the method have uneven particle size distribution and large energy consumption.
The eutectic salt is a eutectic mixture, also called eutectic ionic liquid, is a mixture formed by two or more substances and has a melting point lower than that of any one of the components, and is usually prepared by compounding quaternary ammonium salt and organic matters. The eutectic mixture has the characteristics of typical ionic liquid, can be used as a solvent at room temperature, is low in price, is easier to prepare and store, and can be used as a solvent for ionothermal synthesis. The ionic thermal synthesis is thermal synthesis by taking ionic liquid such as eutectic salt as a solvent, the ionic liquid is not only a solvent, but also a surfactant and a template agent in the ionic thermal synthesis process, and the synthesis method is a novel method for synthesizing the lithium battery positive electrode material. The appearance of the product of the ionothermal synthesis is correspondingly changed due to different anions in the ionic liquid, and is also different due to different lengths of the cationic chains.
Therefore, the lithium battery anode material with high crystallinity and various forms can be prepared at a lower temperature by an ionothermal synthesis method, a wider research field is provided for scientific research work, and the method has good scientific and practical significance.
Disclosure of Invention
The present invention has been made to overcome the above problems occurring in the conventional art, and an object of the present invention is to provide a method for preparing an electrode material using a eutectic salt.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a method for preparing an electrode material using a eutectic salt, comprising the steps of:
1) preparation of eutectic salt: selecting choline chloride as a hydrogen bond acceptor, selecting at least one of ethylene glycol, urea, oxalic acid and citric acid as a hydrogen bond donor, mixing the hydrogen bond acceptor and the hydrogen bond donor, stirring, and standing to obtain a transparent and uniform eutectic ionic liquid;
2) preparing an electrode material: eutectic ionic liquid and Li3PO4Sequentially adding the powder and a manganese source into an application container, stirring for 10min, transferring into a polytetrafluoroethylene lining, then putting the polytetrafluoroethylene lining into a hydrothermal kettle, carrying out hydrothermal reaction for 10-30h at the temperature of 180-220 ℃, centrifuging, removing upper-layer liquid, then respectively carrying out centrifugal washing by deionized water and ethanol, obtaining powder after washing, drying the powder for 8-16h at the temperature of 70-90 ℃, and obtaining lithium manganese phosphate capable of being used as an electrode material after drying.
Further, the method for preparing an electrode material using the eutectic salt, the Li, as described above3PO4The powder is prepared by a coprecipitation method.
Further, the method for preparing the electrode material using the eutectic salt as described above, the manganese source is one of manganese sulfate, manganese acetate and manganese chloride, and Li3PO4The stoichiometric ratio of the medium Li to the Mn in the manganese source is 1: 1.
Further, in the method for preparing an electrode material using the eutectic salt as described above, the centrifugal washing is performed 6 times in total, and the centrifugal washing is performed 4 times with deionized water and then 2 times with ethanol.
Further, according to a preferred embodiment of the present invention, the hydrogen bond donor is ethylene glycol, and the molar ratio of choline chloride to ethylene glycol is 1: 3.
further, in a preferred embodiment of the present invention, the hydrogen bond donor is urea, and the molar ratio of choline chloride to urea is 2: 1.
further, according to a preferred embodiment of the present invention, the hydrogen bond donor is oxalic acid, and the molar ratio of choline chloride to oxalic acid is 2: 1.
further, according to a preferred embodiment of the present invention, the hydrogen bond donor is citric acid, and the molar ratio of choline chloride to citric acid is 1: 1.
further, according to a preferred embodiment of the present invention, the hydrogen bond donor is ethylene glycol and urea, and the molar ratio of choline chloride, ethylene glycol and urea is 1:3: 1.
further, in a preferred embodiment of the present invention, the hydrogen bond donor is ethylene glycol and oxalic acid, and the molar ratio of choline chloride, ethylene glycol and oxalic acid is 1:3: 1.
the invention has the beneficial effects that:
the method has scientific and reasonable design, and the lithium manganese phosphate serving as the anode material of the lithium ion battery is prepared by using the eutectic salt as the template, so that a brand new thought is provided for the preparation of the lithium manganese phosphate, and a wider research field is provided for scientific research work; the method has the advantages of environmental protection and simple process, and the prepared product has smaller charge transfer and ion diffusion resistance and shows excellent electrochemical performance.
Of course, it is not necessary for any one product that embodies the invention to achieve all of the above advantages simultaneously.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is an SEM photograph of a positive electrode material lithium manganese phosphate in example 1;
FIG. 2 is an XRD pattern of lithium manganese phosphate as a positive electrode material in example 1;
FIG. 3 is an SEM photograph of a positive electrode material lithium manganese phosphate in example 2;
FIG. 4 is an XRD pattern of lithium manganese phosphate as a positive electrode material in example 2;
FIG. 5 is an SEM photograph of a positive electrode material lithium manganese phosphate in example 3;
FIG. 6 is an XRD pattern of lithium manganese phosphate as a positive electrode material in example 3;
FIG. 7 is an SEM photograph of a positive electrode material lithium manganese phosphate in example 4;
FIG. 8 is an XRD pattern of lithium manganese phosphate as a positive electrode material in example 4;
FIG. 9 is an SEM photograph of a positive electrode material lithium manganese phosphate in example 5;
fig. 10 is an XRD pattern of lithium manganese phosphate as the cathode material in example 5.
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.
Example 1
In a fume hood, choline chloride and ethylene glycol are prepared into a mixed solution according to a certain molar ratio of 1:3, wherein the choline chloride is 13.96g, and the ethylene glycol is 18.6 g. And (3) moving the beaker filled with the mixture of the choline chloride and the glycol to a water bath kettle at 70 ℃ for standing for 2 hours, and then stirring for 5 hours at the rotating speed of 350r/min under the action of a magnetic stirrer to fully mix the two substances to prepare a transparent and uniform choline chloride/glycol eutectic salt solution.
Heating and stirring 200mL of 0.9mol/L LiOH solution in a water bath kettle at 50 ℃, wherein the rotating speed of a magnetic stirrer is 350 r/min. Then 0.5mol/L of H3PO4100mL of the solution was added dropwise to the above LiOH solution by a peristaltic pump at a rate of 6 mL/min. At this time, white flocculent precipitate was generated, and after the dropwise addition was completed, the solution was allowed to stand for 2 hours. The precipitation product is calcined for 3 hours at 350 ℃ after separation, washing and drying treatment to obtain white Li3PO4And (3) powder.
Measuring 70mL of the transparent and uniform choline chloride/ethylene glycol eutectic salt solution in a beaker with the capacity of 100mL, and preparing Li by adopting a coprecipitation method3PO4Powder 10mmol and manganese sulfate 10mmol were added to the beaker in this order. After magnetic stirring for ten minutes, a polytetrafluoroethylene liner having a capacity of 100mL was poured in. The hydrothermal reaction was carried out at 190 ℃ for 20h, followed by natural cooling to room temperature. Centrifuging at 7500r/min with centrifuge to remove supernatant liquid, washing with ionized water for 4 times, washing with ethanol for 2 times, and drying at 80 deg.C for 12 hr to obtain lithium manganese phosphate.
Example 2
In a fume hood, choline chloride and urea are prepared into a mixed solution according to a certain molar ratio of 2:1, wherein 27.9g of choline chloride and 6.1g of urea are contained in the mixed solution. And (3) moving the beaker filled with the mixture of the choline chloride and the urea to an oil bath kettle at 90 ℃ for standing for 2 hours, and then stirring the mixture for 5 hours at the rotating speed of 350r/min under the action of a magnetic stirrer to fully mix the two substances to prepare a transparent and uniform choline chloride/urea eutectic salt solution.
Heating and stirring 200mL of 0.9mol/L LiOH solution in a water bath kettle at 50 ℃, wherein the rotating speed of a magnetic stirrer is 350 r/min. Then 0.5mol/L of H3PO4100mL of the solution was added dropwise to the above LiOH solution by a peristaltic pump at a rate of 6 mL/min. At this time, white flocculent precipitate was generated, and after the dropwise addition was completed, the solution was allowed to stand for 2 hours. The precipitation product is calcined for 3 hours at 350 ℃ after separation, washing and drying treatment to obtain white Li3PO4And (3) powder.
Measuring 70mL of the transparent and uniform choline chloride/urea eutectic salt solution in a beaker with the capacity of 100mL, and preparing Li by adopting a coprecipitation method3PO4Powder 10mmol and manganese acetate 10mmol are added to the beaker in sequence. After magnetic stirring for ten minutes, a polytetrafluoroethylene liner having a capacity of 100mL was poured in. The hydrothermal reaction was carried out at 210 ℃ for 20h, followed by natural cooling to room temperature. Centrifuging at 7500r/min with centrifuge to remove supernatant liquid, washing with ionized water for 4 times, washing with ethanol for 2 times, and drying at 80 deg.C for 12 hr to obtain lithium manganese phosphate.
Example 3
In a fume hood, choline chloride and oxalic acid are prepared into a mixed solution according to a certain molar ratio of 2:1, wherein the choline chloride accounts for 27.9g, and the oxalic acid accounts for 9.1 g. And (3) moving the beaker filled with the mixture of the choline chloride and the oxalic acid into an oil bath kettle at the temperature of 90 ℃ for standing for 2 hours, and then stirring the mixture for 5 hours at the rotating speed of 350r/min under the action of a magnetic stirrer to fully mix the two substances to prepare a transparent and uniform choline chloride/oxalic acid eutectic salt solution.
Heating and stirring 200mL of 0.9mol/L LiOH solution in a water bath kettle at 50 ℃, wherein the rotating speed of a magnetic stirrer is 350 r/min. Then 0.5mol/L of H3PO4100mL of the solution was added dropwise to the above LiOH solution by a peristaltic pump at a rate of 6 mL/min. At this time, white flocculent precipitate was generated, and after the dropwise addition was completed, the solution was allowed to stand for 2 hours. The precipitation product is calcined for 3 hours at 350 ℃ after separation, washing and drying treatment to obtain white Li3PO4And (3) powder.
Measuring 70mL of the transparent and uniform choline chloride/oxalic acid eutectic salt solution in a beaker with the capacity of 100mL, and preparing Li by adopting a coprecipitation method3PO410mmol of the powder and 10mmol of manganese chloride are added to the beaker in this order. After magnetic stirring for ten minutes, a polytetrafluoroethylene liner having a capacity of 100mL was poured in. The hydrothermal reaction was carried out at 220 ℃ for 20h, followed by natural cooling to room temperature. Centrifuging at 7500r/min with centrifuge to remove upper layer liquid, centrifuging and washing with deionized water for 4 times, centrifuging and washing with ethanol for 2 times, and drying the obtained powder at 80 deg.C for 12h to obtain lithium manganese phosphate.
Example 4
In a fume hood, choline chloride and citric acid are prepared into a mixed solution according to a certain molar ratio of 1:1, wherein the choline chloride is 13.96g, and the oxalic acid is 19.2 g. And (3) moving the beaker filled with the mixture of the choline chloride and the citric acid into an oil bath kettle at the temperature of 90 ℃ for standing for 2 hours, and then stirring the mixture for 5 hours at the rotating speed of 350r/min under the action of a magnetic stirrer to fully mix the two substances to prepare a transparent and uniform choline chloride/citric acid eutectic salt solution.
Heating and stirring 200mL of 0.9mol/L LiOH solution in a water bath kettle at 50 ℃, wherein the rotating speed of a magnetic stirrer is 350 r/min. Then 0.5mol/L of H3PO4100mL of the solution was added dropwise to the above LiOH solution by a peristaltic pump at a rate of 6 mL/min. At this time, white flocculent precipitate was generated, and after the dropwise addition was completed, the solution was allowed to stand for 2 hours. The precipitation product is calcined for 3 hours at 350 ℃ after separation, washing and drying treatment to obtain white Li3PO4And (3) powder.
Measuring 70mL of the transparent and uniform choline chloride/citric acid eutectic salt solution into a beaker with the capacity of 100mL, and preparing Li by adopting a coprecipitation method3PO410mmol of powder and 10mmol of manganese sulfate are added into the beaker in sequence. After magnetic stirring for ten minutes, a polytetrafluoroethylene liner having a capacity of 100mL was poured in. The mixture was subjected to hydrothermal reaction at 200 ℃ for 20 hours, followed by natural cooling to room temperature. Centrifuging at 7500r/min with centrifuge to remove upper layer liquid, centrifuging and washing with deionized water for 4 times, centrifuging and washing with ethanol for 2 times, and drying the obtained powder at 80 deg.C for 12h to obtain lithium manganese phosphate.
Example 5
In a fume hood, choline chloride, ethylene glycol and urea are prepared into a mixed solution according to a certain molar ratio of 1:3:1, wherein the choline chloride is 13.96g, the ethylene glycol is 18.6g and the urea is 6.1 g. And (3) moving the beaker filled with the mixture of choline chloride, glycol and urea to a water bath kettle at 70 ℃ for standing for 2h, and then stirring for 5h at the rotating speed of 350r/min under the action of a magnetic stirrer to fully mix the two substances to prepare a transparent and uniform choline chloride/glycol/urea eutectic salt solution.
Heating and stirring 200mL of 0.9mol/L LiOH solution in a water bath kettle at 50 ℃, wherein the rotating speed of a magnetic stirrer is 350 r/min. Then, 100mL of a 0.5mol/L H3PO4 solution was added dropwise to the above LiOH solution by a peristaltic pump at a rate of 6 mL/min. At this time, white flocculent precipitate was generated, and after the dropwise addition was completed, the solution was allowed to stand for 2 hours. The precipitation product is calcined for 3 hours at 350 ℃ after separation, washing and drying treatment, and white Li3PO4 powder is obtained.
Measuring 70mL of the transparent and uniform choline chloride/ethylene glycol/urea eutectic salt solution into a beaker with the capacity of 100mL, and sequentially adding 10mmol of Li3PO4 powder and 10mmol of manganese sulfate which are prepared by a coprecipitation method into the beaker. After magnetic stirring for ten minutes, a polytetrafluoroethylene liner having a capacity of 100mL was poured in. The hydrothermal reaction was carried out at 210 ℃ for 20h, followed by natural cooling to room temperature. Centrifuging at 7500r/min with centrifuge to remove upper layer liquid, centrifuging and washing with deionized water for 4 times, centrifuging and washing with ethanol for 2 times, and drying the obtained powder at 80 deg.C for 12h to obtain lithium manganese phosphate.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A method for preparing an electrode material by using eutectic salt is characterized by comprising the following steps:
1) preparation of eutectic salt: selecting choline chloride as a hydrogen bond acceptor, selecting at least one of ethylene glycol, urea, oxalic acid and citric acid as a hydrogen bond donor, mixing the hydrogen bond acceptor and the hydrogen bond donor, stirring, and standing to obtain a transparent and uniform eutectic ionic liquid;
2) preparing an electrode material: eutectic ionic liquid and Li3PO4Sequentially adding the powder and the manganese sourceStirring the mixture in a reaction container for 10min, transferring the mixture to a polytetrafluoroethylene lining, then putting the polytetrafluoroethylene lining into a hydrothermal kettle, carrying out hydrothermal reaction for 10-30h at the temperature of 180-220 ℃, centrifuging and removing upper-layer liquid, then respectively carrying out centrifugal washing by deionized water and ethanol to obtain powder after washing, drying the powder for 8-16h at the temperature of 70-90 ℃, and drying to obtain the lithium manganese phosphate capable of being used as an electrode material.
2. The method for preparing an electrode material using a eutectic salt according to claim 1, wherein: the Li3PO4The powder is prepared by a coprecipitation method.
3. The method for preparing an electrode material using a eutectic salt according to claim 1, wherein: the manganese source is one of manganese sulfate, manganese acetate and manganese chloride, and Li3PO4The stoichiometric ratio of the medium Li to the Mn in the manganese source is 1: 1.
4. The method for preparing an electrode material using a eutectic salt according to claim 1, wherein: the centrifugal washing is carried out for 6 times, firstly, deionized water is used for centrifugal washing for 4 times, and then, ethanol is used for centrifugal washing for 2 times.
5. The method for preparing an electrode material using a eutectic salt according to any one of claims 1 to 4, wherein: the hydrogen bond donor is ethylene glycol, and the molar ratio of the choline chloride to the ethylene glycol is 1: 3.
6. the method for preparing an electrode material using a eutectic salt according to any one of claims 1 to 4, wherein: the hydrogen bond donor is urea, and the mol ratio of the choline chloride to the urea is 2: 1.
7. the method for preparing an electrode material using a eutectic salt according to any one of claims 1 to 4, wherein: the hydrogen bond donor is oxalic acid, and the molar ratio of the choline chloride to the oxalic acid is 2: 1.
8. the method for preparing an electrode material using a eutectic salt according to any one of claims 1 to 4, wherein: the hydrogen bond donor is citric acid, and the molar ratio of the choline chloride to the citric acid is 1: 1.
9. the method for preparing an electrode material using a eutectic salt according to any one of claims 1 to 4, wherein: the hydrogen bond donor is ethylene glycol and urea, and the molar ratio of the choline chloride to the ethylene glycol to the urea is 1:3: 1.
10. the method for preparing an electrode material using a eutectic salt according to any one of claims 1 to 4, wherein: the hydrogen bond donor is ethylene glycol and oxalic acid, and the molar ratio of the choline chloride to the ethylene glycol to the oxalic acid is 1:3: 1.
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