CN111960398A - Preparation method of lithium monofluorophosphate - Google Patents
Preparation method of lithium monofluorophosphate Download PDFInfo
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- CN111960398A CN111960398A CN202010883209.2A CN202010883209A CN111960398A CN 111960398 A CN111960398 A CN 111960398A CN 202010883209 A CN202010883209 A CN 202010883209A CN 111960398 A CN111960398 A CN 111960398A
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- lithium
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- lithium monofluorophosphate
- monofluorophosphate
- vacuum
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- SXWUDUINABFBMK-UHFFFAOYSA-L dilithium;fluoro-dioxido-oxo-$l^{5}-phosphane Chemical compound [Li+].[Li+].[O-]P([O-])(F)=O SXWUDUINABFBMK-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 20
- DWYMPOCYEZONEA-UHFFFAOYSA-N fluorophosphoric acid Chemical compound OP(O)(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-N 0.000 claims abstract description 18
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 239000011737 fluorine Substances 0.000 claims abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 9
- 229910000792 Monel Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 5
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 4
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 229910001026 inconel Inorganic materials 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 21
- 229910045601 alloy Inorganic materials 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 6
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910018819 PO3F Inorganic materials 0.000 description 4
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- QTZBTBLHYPSFMG-UHFFFAOYSA-N 5-chloro-3-methylpyridin-2-amine Chemical compound CC1=CC(Cl)=CN=C1N QTZBTBLHYPSFMG-UHFFFAOYSA-N 0.000 description 2
- 229910008963 Li2PO3F Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940074371 monofluorophosphate Drugs 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- C01B25/455—Phosphates containing halogen
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- C01P2006/80—Compositional purity
-
- 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 preparation method of lithium monofluorophosphate, which comprises the following steps: s1, preparation of monofluorophosphoric acid: taking phosphorus pentoxide and hydrofluoric acid to react in a fluorine-resistant closed reaction container to obtain monofluorophosphoric acid; s2, separating and purifying the product in the S1 step through vacuum distillation; s3, searching a lithium source to react with the product obtained in the step S2, evaporating, concentrating and crystallizing the reacted solution to obtain a crystal, namely lithium monofluorophosphate, and drying the crystal in vacuum to obtain a lithium monofluorophosphate product; the mass fraction of the hydrofluoric acid is between 65 and 75 percent; the material of the fluorine-resistant closed reaction vessel can be one of titanium-nickel alloy, hastelloy, Monel alloy and Engkel alloy; the fluorine-resistant closed reaction container in the step S1 is provided with a solid and liquid feeding device; the invention has simple process, few by-products, easy initiation of reaction and high product purity.
Description
Technical Field
The invention relates to the technical field of preparation of lithium monofluorophosphate, in particular to a preparation method of lithium monofluorophosphate.
Background
With the rapid development of lithium ion batteries, lithium ion batteries have been rapidly applied to a plurality of fields such as electricity, automobiles, aerospace and the like, but the decomposition and side reaction of electrolyte in the use process of conventional lithium ion batteries have bad influence on the durability, such as cyclicity, high-temperature storage performance and the like, and cannot meet the increasingly high requirements of high and low temperature performance, battery capacity, cyclicity and the like of the lithium ion batteries in the current market, so that the development of various electrolyte additives with excellent performance is urgent. The lithium monofluorophosphate as the lithium ion battery additive can obviously improve the low-temperature characteristic and the cycling stability of the lithium ion secondary battery. Therefore, under the background that the market scale of the portable mobile equipment and the new energy automobile is continuously enlarged at present, the demand of lithium monofluorophosphate as an electrolyte additive of a high-performance battery and a storage battery is increased correspondingly.
In Japanese patent CN102983359A, Li2PO3F and LiPO2F2The storage characteristics of a secondary battery composed of an electrolyte solution added as an auxiliary compound have been studied in detail. The study shows that under the same electrolyte composition condition, the cycle retention rate of the secondary battery is about 75-77% without adding the auxiliary compound, the preservation maintenance rate is 80-81%, and 2% of the auxiliary compound Li is added2PO3After F, the cycle retention rate of the secondary battery can reach 86%, and the preservation maintenance rate is 92%. Therefore, the cycle performance and the durability of the lithium battery can be greatly improved by a small amount of electrolyte additive.
In view of these drawbacks, it is necessary to design a method for preparing lithium monofluorophosphate.
Disclosure of Invention
The invention aims to provide a preparation method of lithium monofluorophosphate, which has the advantages of simple process method, less by-products, easy initiation of reaction and high product purity.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of lithium monofluorophosphate comprises the following steps:
s1, preparation of monofluorophosphoric acid: taking phosphorus pentoxide and hydrofluoric acid to react in a fluorine-resistant closed reaction container to obtain monofluorophosphoric acid;
s2, separating and purifying the product in the S1 step through vacuum distillation;
s3, searching a lithium source to react with the product obtained in the step S2, evaporating, concentrating and crystallizing the reacted solution to obtain a crystal, namely lithium monofluorophosphate, and drying the crystal in vacuum to obtain the lithium monofluorophosphate product.
As a further scheme of the invention: the mass fraction of the hydrofluoric acid is between 65 and 75 percent.
As a further scheme of the invention: the material of the fluorine-resistant closed reaction vessel can be one of titanium-nickel alloy, hastelloy, Monel alloy and England alloy.
As a further scheme of the invention: and the fluorine-resistant closed reaction container in the step S1 is provided with a solid and liquid feeding device.
As a further scheme of the invention: and introducing nitrogen to maintain the system temperature in the reaction process in the step S1, wherein the system temperature is controlled at-10 ℃ and the reaction time is 2 h.
As a further scheme of the invention: the mole ratio of the phosphorus pentoxide to the hydrofluoric acid in the step S1 is preferably 1: 2-1: 2.1.
as a further scheme of the invention: the vacuum degree of vacuum distillation separation in the step S2 is preferably 0-0.05MPa, the temperature is preferably 110-120 ℃, and the reduced pressure distillation time is 30 min.
As a further scheme of the invention: the lithium source in the step S3 may be one selected from lithium oxide, lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate, and lithium chloride.
As a further scheme of the invention: and in the step S3, the reaction temperature is controlled to be 50-100 ℃ and the reaction time is 2 h.
As a further scheme of the invention: in the step S3, the evaporation, concentration and crystallization temperatures are controlled to be 100-150 ℃, the vacuum drying temperature is preferably 150-180 ℃, the vacuum degree is preferably 0-0.1MPa, and the time is set to be 3 h.
The invention has the beneficial effects that: s1, preparation of monofluorophosphoric acid: taking phosphorus pentoxide and hydrofluoric acid to react in a fluorine-resistant closed reaction container to obtain monofluorophosphoric acid;wherein, hydrofluoric acid preparation: firstly, preparing hydrofluoric acid with the mass fraction of 65-75% for later use, firstly taking pure water into a polytetrafluoroethylene plastic barrel according to the concentration ratio, then slowly adding a corresponding amount of hydrofluoric acid, and uniformly stirring; wherein phosphorus pentoxide and hydrofluoric acid are used as raw materials, and the reaction molar ratio is n (P)2O5): n (hf) ═ 1: 2-1: 2.05, putting a certain amount of phosphorus pentoxide into a sealed Monel alloy reaction container, then uniformly pumping 69% of hydrofluoric acid into the reaction container through a peristaltic pump, introducing nitrogen gas in the reaction process to maintain the temperature of the reaction environment at-10 ℃, and keeping the reaction for 2 hours, wherein tail gas is absorbed in the reaction process, and the following reactions mainly occur in the process: p2O5+2HF+H2O＝2H2PO3F, the main product of the reaction is monofluorophosphoric acid, the byproducts mainly comprise a small amount of difluorophosphoric acid and hydrofluoric acid, when the reaction is finished, the distillation temperature is set to be 110-120 ℃, the vacuum degree is 0-0.05MPa, the reduced pressure distillation is carried out for 30min, the evaporated gas is absorbed by alkali liquor, and the distillation residue is high-purity monofluorophosphoric acid; s2, separating and purifying the product in the S1 step by vacuum distillation; s3, searching a lithium source to react with the product obtained in the step S2, evaporating, concentrating and crystallizing the reacted solution to obtain a crystal, namely lithium monofluorophosphate, and drying the crystal in vacuum to obtain a lithium monofluorophosphate product; the process is simple, less in side product, easy to initiate reaction and high in product purity.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood 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.
The technical scheme of the invention is as follows: a preparation method of lithium monofluorophosphate comprises the following steps:
s1, preparation of monofluorophosphoric acid: taking phosphorus pentoxide and hydrofluoric acid to react in a fluorine-resistant closed reaction container to obtain monofluorophosphoric acid;
wherein, hydrofluoric acid preparation: firstly, preparing hydrofluoric acid with the mass fraction of 65-75% for later use, firstly taking pure water into a polytetrafluoroethylene plastic barrel according to the concentration ratio, then slowly adding a corresponding amount of hydrofluoric acid, and uniformly stirring;
wherein phosphorus pentoxide and hydrofluoric acid are used as raw materials, and the reaction molar ratio is n (P)2O5): n (hf) ═ 1: 2-1: 2.05, putting a certain amount of phosphorus pentoxide into a sealed Monel alloy reaction container, then uniformly pumping 69% of hydrofluoric acid into the reaction container through a peristaltic pump, introducing nitrogen gas in the reaction process to maintain the temperature of the reaction environment at-10 ℃, and keeping the reaction for 2 hours, wherein tail gas is absorbed in the reaction process, and the following reactions mainly occur in the process: p2O5+2HF+H2O＝2H2PO3F, the main product of the reaction is monofluorophosphoric acid, the byproducts mainly comprise a small amount of difluorophosphoric acid and hydrofluoric acid, when the reaction is finished, the distillation temperature is set to be 110-120 ℃, the vacuum degree is 0-0.05MPa, the reduced pressure distillation is carried out for 30min, the evaporated gas is absorbed by alkali liquor, and the distillation residue is high-purity monofluorophosphoric acid;
s2, separating and purifying the product in the S1 step by vacuum distillation;
s3, searching a lithium source to react with the product obtained in the step S2, evaporating, concentrating and crystallizing the reacted solution to obtain a crystal, namely lithium monofluorophosphate, and drying the crystal in vacuum to obtain a lithium monofluorophosphate product;
wherein the monofluorophosphoric acid and a suitable lithium source are selected in accordance with n (Li)+)：n(H2PO3F) 2: 1-2: 1.05, putting the mixture into a reaction vessel, and fully stirring, wherein the reaction in the process is as follows: 2Li++PO3F2-→Li2PO3F, after the reaction is finished, taking the reaction solution for evaporation, concentration and crystallization, and drying to obtain a finished lithium monofluorophosphate;
wherein, the material of the fluorine-resistant closed reaction vessel can be one of titanium-nickel alloy, hastelloy, Monel alloy and Enkeel alloy;
wherein, the sealed reaction container made of fluorine-resistant materials in the step S1 is provided with a solid and liquid feeding device;
wherein, nitrogen is introduced to maintain the temperature of the system in the reaction process in the step S1, the temperature of the system is controlled to be-10 ℃ and the reaction time is 2 h;
wherein, the mole ratio of the phosphorus pentoxide to the hydrofluoric acid in the step of S1 is preferably 1: 2-1: 2.1;
wherein the vacuum degree of the vacuum distillation separation in the step S2 is preferably 0-0.05MPa, the temperature is preferably 110-120 ℃, and the reduced pressure distillation time is 30 min;
wherein, the lithium source in the step S3 may be selected from one of lithium oxide, lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate, and lithium chloride;
wherein the reaction temperature in the step S3 is controlled to be 50-100 ℃ and the reaction time is 2 h;
wherein, the evaporation, concentration and crystallization temperature in the step S3 is controlled to be 100-150 ℃, the vacuum drying temperature is preferably 150-180 ℃, the vacuum degree is preferably 0-0.1MPa, and the time is set to be 3 h.
Example 1:
firstly, 710g of phosphorus pentoxide is put in a sealed Monel alloy reaction container, 310g of prepared hydrofluoric acid is pumped into the reaction container at a constant speed through a peristaltic pump, nitrogen is introduced in the reaction process to maintain the temperature of the system at-10 ℃, the reaction is carried out for 2h, the reaction is finished, the temperature is raised to 110-120 ℃, the vacuum degree is adjusted to 0-0.05MPa, the distillation time is 30min, the tail part of the reaction container is connected with an alkali liquor tail gas absorption device, and 968g of monofluorophosphoric acid is obtained by weighing after the reaction is finished;
in example 1, experiments were carried out with different concentrations of hydrofluoric acid, and comparison was carried out by calculating the yield and purity of monofluorophosphoric acid, and the experimental data were as follows:
example 2
Selecting a lithium source as LiOH, putting 432g of lithium hydroxide into a reaction container, introducing 900g of monofluorophosphoric acid in the step S1 into the reaction container, heating and stirring the mixture, maintaining the reaction temperature at 50-100 ℃, reacting for 2 hours, raising the temperature to 100-150 ℃ after the reaction is completely finished until the water is evaporated to dryness, drying the crystallized product in a vacuum drying box at the set temperature of 180-220 ℃ for 3 hours to obtain 930g of lithium monofluorophosphate, wherein the yield is 92.3%.
Example 3
Putting 270g of lithium oxide into a reaction container, introducing 900g of monofluorophosphate in the step S1 into the reaction container, heating while stirring, maintaining the reaction temperature at 50-100 ℃, reacting for 2h, raising the temperature to 100-150 ℃ after the reaction is completely finished until the water is evaporated to dryness, drying a crystallized product in a vacuum drying oven at the set temperature of 180-220 ℃ for 3h to obtain 933g of lithium monofluorophosphate, wherein the yield is 92.6%.
Example 4
And (2) putting 666g of lithium carbonate into a reaction container, introducing 900g of monofluorophosphate in the step S1 into the reaction container, heating while stirring, maintaining the reaction temperature at 50-100 ℃, reacting for 2h, raising the temperature to 100-150 ℃ after the reaction is completely finished until the water is evaporated to dryness, drying the crystallized product in a vacuum drying oven at the set temperature of 180-220 ℃ for 3h to obtain 900g of lithium monofluorophosphate, wherein the yield is 89.3%.
In conclusion, the process method is simple, few in byproducts, easy to initiate reaction and high in product purity.
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 preparation method of lithium monofluorophosphate is characterized by comprising the following steps:
s1, preparation of monofluorophosphoric acid: taking phosphorus pentoxide and hydrofluoric acid to react in a fluorine-resistant closed reaction container to obtain monofluorophosphoric acid;
s2, separating and purifying the product in the S1 step through vacuum distillation;
s3, searching a lithium source to react with the product obtained in the step S2, evaporating, concentrating and crystallizing the reacted solution to obtain a crystal, namely lithium monofluorophosphate, and drying the crystal in vacuum to obtain the lithium monofluorophosphate product.
2. The method for preparing lithium monofluorophosphate according to claim 1, wherein the hydrofluoric acid is contained in an amount of 65 to 75% by mass.
3. The method for preparing lithium monofluorophosphate according to claim 1, wherein the fluorine-resistant closed reaction vessel is made of one material selected from the group consisting of a titanium-nickel alloy, hastelloy, monel and inconel.
4. The method for preparing lithium monofluorophosphate according to claim 1, wherein the fluorine-resistant sealed reaction vessel in the step S1 is equipped with a solid/liquid feeding device.
5. The method for preparing lithium monofluorophosphate according to claim 1, wherein nitrogen is introduced during the reaction in the step S1 to maintain the system temperature, which is controlled to be-10 ℃ to 10 ℃ and the reaction time is 2 hours.
6. The method for preparing lithium monofluorophosphate according to claim 1, wherein the molar ratio of phosphorus pentoxide to hydrofluoric acid in the step S1 is preferably 1: 2-1: 2.1.
7. the method for preparing lithium monofluorophosphate according to claim 1, wherein the vacuum degree of vacuum distillation separation in the step S2 is preferably 0 to 0.05MPa, the temperature is preferably 110 to 120 ℃, and the vacuum distillation time is 30 min.
8. The method for preparing lithium monofluorophosphate according to claim 1, wherein the lithium source in the step S3 can be selected from one of lithium oxide, lithium hydroxide, lithium carbonate, lithium oxalate, lithium acetate and lithium chloride.
9. The method for preparing lithium monofluorophosphate according to claim 1, wherein the reaction temperature in the step S3 is controlled to be 50 to 100 ℃ and the reaction time is 2 hours.
10. The method for preparing lithium monofluorophosphate according to claim 1, wherein the evaporation, concentration and crystallization temperature in the step S3 is controlled to 100 to 150 ℃, the vacuum drying temperature is preferably 150 to 180 ℃, the degree of vacuum is preferably 0 to 0.1MPa, and the time is set to 3 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114084881A (en) * | 2021-11-08 | 2022-02-25 | 厦门海辰新能源科技有限公司 | Method for preparing lithium monofluorophosphate, electrolyte and lithium battery |
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| US4374108A (en) * | 1979-11-22 | 1983-02-15 | Central Glass Company, Limited | Process of preparing alkali monofluorophosphate |
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2020
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|---|---|---|---|---|
| CA445265A (en) * | 1947-11-25 | Lange Willy | Anhydrous monofluorophosphoric acid | |
| US2408785A (en) * | 1944-06-28 | 1946-10-08 | Ozark Chemical Company | Method of production of anhydrous monofluorophosphoric acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114084881A (en) * | 2021-11-08 | 2022-02-25 | 厦门海辰新能源科技有限公司 | Method for preparing lithium monofluorophosphate, electrolyte and lithium battery |
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