CN114507257B - Fluorinated cyclic phosphorus-containing molecule and application thereof - Google Patents

Fluorinated cyclic phosphorus-containing molecule and application thereof Download PDF

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CN114507257B
CN114507257B CN202110632731.8A CN202110632731A CN114507257B CN 114507257 B CN114507257 B CN 114507257B CN 202110632731 A CN202110632731 A CN 202110632731A CN 114507257 B CN114507257 B CN 114507257B
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郑奇峰
丁奎
邹汉琴
赖嘉伟
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South China Normal University
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Abstract

The invention belongs to the technical field of new battery materials, and particularly relates to a fluorinated cyclic phosphorus-containing molecule and application thereof. In the fluorinated cyclic phosphorus-containing molecules, a fluorinated group can form a stable inorganic SEI film in the battery charging and discharging process and can improve the solvent oxidation resistance, and an elastic organic SEI film can be formed by ring-opening polymerization in the battery circulation process in the cyclic structure of the fluorinated cyclic phosphorus-containing molecules, so that the volume effect of an electrode material in the charging and discharging process is effectively slowed down, and when the fluorinated cyclic phosphorus-containing molecules are used in a solvent or an additive in a nonaqueous secondary battery electrolyte, the high-pressure resistance and safety of the battery can be effectively improved, the popularization and application of the high-specific-energy high-safety long-cycle secondary battery in the field of electric automobiles are facilitated, the defects of various performances of the conventional secondary battery electrolyte are overcome, and the problems of high manufacturing and using costs are solved; the synthetic method of the fluorinated cyclic molecule is simple, safe to operate, high in product purity, excellent in performance in secondary batteries such as lithium/sodium ion batteries and the like, and suitable for wide application.

Description

Fluorinated cyclic phosphorus-containing molecule and application thereof
Technical Field
The invention belongs to the technical field of new battery materials, and particularly relates to a fluorinated cyclic phosphorus-containing molecule and application thereof.
Background
With the large-scale appearance and rapid development of wearable and portable electronic products, electric automobiles, renewable energy conversion technologies and the like, higher requirements are put on the energy and power density, the cycle life, the safety, the reliability and the like of energy storage devices. Compared with the research on the anode and cathode materials of the lithium ion battery, the research on the electrolyte is relatively lagged, but the electrolyte has great influence on the high voltage resistance, the cycle stability, the quick charge, the safety performance and the like of the battery. Currently, the electrolyte used in commercial lithium ion batteries is still 1M lithium hexafluorophosphate (LiPF) 6 ) Dissolving in a mixture of cyclic Ethylene Carbonate (EC) with large dielectric constant and chain carbonate (such as dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, etc.)In the preparation. However, this solvent system has poor high pressure resistance (<4.4V) poor high temperature resistance: (<55 ℃, low flash point (25 ℃), easy combustion and the like, and can not meet the development requirements of high energy density and high safety of the lithium ion battery.
The chain phosphate is used as a common flame retardant additive and is the best choice for serving as an electrolyte additive of a high-voltage-resistant battery. In general, phosphorus atoms in phosphate ester are trapping agents of hydrogen radicals, which are the main reasons for initiating chain reaction to cause combustion, and the phosphate ester can play a certain flame retardant effect, but the organic chain phosphate ester can not form a stable Solid Electrolyte Interface (SEI) film on the surface of a graphite anode, so that graphite falls off in the first charging process and electrolyte is continuously decomposed, and the cycling stability of the battery is very poor. Therefore, organic phosphates are introduced into the electrolyte as flame retardant additives to balance the battery performance and the incombustibility of the electrolyte. In order to further increase the amount of the non-flammable phosphate-based solvent, an SEI film-forming additive is generally required to compensate for the battery performance, thus greatly reducing the energy density of the battery.
Research shows that introduction of fluoro groups into electrolyte solvent molecules can significantly improve oxidation and reduction stability of the electrolyte and is beneficial to formation of a stable SEI film. However, the electrolyte solution commercialized at present has low flash point and is easy to burn after introduction of fluoro groups, and a plurality of solvents are mixed, which is not favorable for exerting the energy density of the secondary battery.
Therefore, in view of the above problems, the present invention aims to provide a fluorinated cyclic phosphorus-containing solvent molecule as a secondary battery electrolyte solvent or additive material to improve the performance of the battery.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a fluorocyclic phosphorus-containing molecule, which is used as a novel material in a solvent or an additive in a non-aqueous secondary battery electrolyte, and combines flame retardant properties and stable positive and negative SEI films when used, so that a single solvent molecule can realize multifunctional properties, and applications thereof.
The technical content of the invention is as follows:
the invention relates to a fluorinated cyclic phosphorus-containing molecule, the structure of which comprises one of a general formula (I), a general formula (II) and a general formula (III), and the molecule is shown as follows:
Figure BDA0003104317170000031
wherein R in the general formulae (I) to (III) 1 ～R 7 Comprises one or any combination of the following steps:
(1) a thiol group having 1 to 5 hydrogen atoms or fluorine atoms or carbon atoms;
(2) a fluorine-substituted alkyl group having 1 to 5 carbon atoms, an alkenyl group branched or straight chain;
(3) fluorine substituted ether with 1-5 carbon atoms, fluorine substituted amino and fluorine substituted sulfonic acid, wherein the fluorine substitution comprises partial substitution and total substitution;
the thiol group comprises ethanethiol.
Further, R 1 One comprising the following groups:
Figure BDA0003104317170000032
further, R in the general formula (I) 2 ～R 5 One comprising the following groups:
Figure BDA0003104317170000041
R 2 ～R 5 at least one of which is a fluorine-containing substituent and not all of which are fluoro groups.
Further, R in the general formula (II) 2 ～R 7 One comprising the following groups:
Figure BDA0003104317170000042
R 2 ～R 7 at least one of which is a fluorine-containing substituent and not all of which are fluoro groups.
Further, R in the general formula (III) 2 ～R 5 One comprising the following groups:
Figure BDA0003104317170000051
R 2 ～R 5 at least one of which is a fluorine-containing substituent and not all of which are fluoro groups.
Further, the fluorinated cyclic phosphorus-containing molecule comprises one of the following molecular structures:
Figure BDA0003104317170000052
Figure BDA0003104317170000061
the invention also provides a fluorinated cyclic phosphorus-containing molecule used as electrolyte or additive of a lithium ion or sodium ion or potassium ion secondary battery;
the lithium salt of the lithium ion secondary battery comprises lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), lithium difluoro (oxalato) borate, and lithium hexafluorophosphate (LiPF) 6 ) Lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium dioxalate borate, lithium perchlorate (LiClO) 4 ) One or more of lithium hexafluoroarsenate;
the sodium salt of the sodium ion secondary battery comprises one or more of sodium bifluorosulfonamide, sodium bistrifluoromethanesulfonamide and sodium hexafluorophosphate;
the potassium salt of the potassium ion secondary battery comprises one or more of potassium bifluorosulfonyl imide, potassium bistrifluoromethanesulfonyl imide and potassium hexafluorophosphate.
The invention also provides a synthetic method of the fluorinated cyclic phosphorus-containing molecule, which comprises the following steps:
1) With PCl 3 After being dissolved, dihydroxy or diamine organic solvent is dripped into the raw materials under the ice bath condition, the mixture reacts at 0 ℃, and a compound x1 is obtained by filtration and distillation;
2) Reacting the compound x1 at high temperature in an organic solution under the condition of introducing oxygen, removing the organic solution after the reaction is finished, and distilling under reduced pressure to obtain a compound x2;
3) Dissolving the compound x2, dripping a thiol solution or a fluorine-containing alcohol solution or a secondary amine solution and triethylamine under an ice bath condition, reacting at 0 ℃, and filtering and distilling to obtain a compound x3;
4) Dissolving a compound x3, dripping a THF (tetrahydrofuran) solution of N-fluoro-diphenyl sulfonamide (NFSI) under an ice bath condition, irradiating ultraviolet light at 0 ℃ for reaction, slowly recovering to room temperature for reaction, and filtering and distilling under reduced pressure after the reaction is finished to obtain a product compound x, namely, a fluoro cyclic phosphorus-containing molecule;
the dihydroxy organic solvent in the step 1) comprises ethylene glycol, trifluoromethyl ethylene glycol, 1, 3-propylene glycol, 2-trifluoromethyl-1, 3-propylene glycol or 1, 3-dihydroxyacetone;
the diamine organic solvent comprises N, N-dimethylethylenediamine or N, N-dimethyl-2-trifluoromethyl-ethylenediamine;
step 2) the organic solution comprises anhydrous toluene.
The invention has the following beneficial effects:
the general structural formula (I-III) of the fluorinated cyclic phosphorus-containing molecule at least contains one fluoro group, and the fluoro group can form a stable inorganic SEI film (LiF) in the process of charging and discharging batteries and can improve the oxidation resistance of a solvent; the general structural formulas (I-III) are all ring structures, and the ring structures can form an elastic organic SEI film through ring opening polymerization in the battery circulation process, so that the volume effect of the electrode material in the charge and discharge process is effectively slowed down; in addition, the structure of the flame-retardant coating contains phosphorus atoms, and the phosphorus elements have better flame-retardant property. In addition, the precise regulation and control are carried out through different structural general formulas, for example, the higher oxygen element proportion in the structural general formula (I) is beneficial to increasing the content of oxygen elements in the SEI so as to reduce the impedance of the SEI film; the proportion of nitrogen elements of the molecules in the general structural formula (III) is increased, and the components of SEI (solid electrolyte interphase) can be accurately regulated and controlled, such as improving the nitrogen content in the SEI so as to improve the stability and reduce the impedance; for example, sulfur-containing molecules in the structure can inhibit the elution of transition metals of the cathode material. The fluorinated cyclic phosphorus-containing molecule can be used as a novel material for a solvent or an additive of a non-aqueous secondary battery electrolyte, can effectively improve the high pressure resistance and safety of the battery, and combines the flame retardant property with the formation of a stable positive and negative SEI film when in use, so that the single solvent molecule realizes the multifunctional characteristic, is favorable for the popularization and application of the secondary battery with high specific energy, high safety and long circulation in the field of electric automobiles, and solves the problems of various performance defects of the existing secondary battery electrolyte and high manufacturing and using costs;
the synthetic method of the fluorinated cyclic molecule is simple, safe to operate, high in product purity, excellent in performance in secondary batteries such as lithium/sodium ions and the like, and suitable for wide application.
Drawings
FIG. 1 is a scheme for the synthesis of Compound 1 of example 1;
FIG. 2 shows nuclear magnetic hydrogen spectrum and fluorine spectrum of Compound 1 of example 1;
FIG. 3 is a scheme for the synthesis of Compound 2 of example 2;
FIG. 4 is a scheme for the synthesis of Compound 3 in example 3;
FIG. 5 is a scheme for the synthesis of Compound 4 in example 4;
FIG. 6 is a scheme for the synthesis of Compound 5 in example 5;
FIG. 7 is a synthetic scheme for Compound 6 of example 6;
FIG. 8 is a scheme for the synthesis of Compound 7 in example 7;
FIG. 9 is a scheme for the synthesis of Compound 8 of example 8;
FIG. 10 is a scheme for the synthesis of Compound 9 in example 9;
FIG. 11 is a scheme for the synthesis of Compound 10 of example 10;
FIG. 12 is a synthetic scheme for Compound 11 of example 11;
FIG. 13 is a synthetic scheme of Compound 12 of example 12;
FIG. 14 is a synthetic scheme for Compound 13 of example 13;
FIG. 15 is a synthetic scheme for Compound 14 of example 14;
FIG. 16 is a synthetic scheme of Compound 32 of example 15;
FIG. 17 is a synthetic scheme of Compound 33 of example 16;
FIG. 18 is a graph of the cycle performance of a graphite | Li cell with a 1M LiFSI electrolyte of compound 1 of example 1;
fig. 19 is a graph of the cycle performance of the NCM111 Li cell with the 1M LiFSI electrolyte of compound 1 in example 1.
Detailed Description
The present invention is described in further detail in the following description of specific embodiments and the accompanying drawings, it is to be understood that these embodiments are merely illustrative of the present invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and modifications thereof by those skilled in the art after reading this disclosure that are equivalent to the above described embodiments.
All the raw materials and reagents of the invention are conventional market raw materials and reagents unless otherwise specified.
Example 1
Preparation of fluorinated cyclic phosphorus-containing molecular compound 1:
1) Synthesis of Compound a1
10.0g (73.6 mmol) of PCl 3 The compound is dissolved in anhydrous Dichloromethane (DCM), 0.99eq of ethylene glycol is slowly dropped under the ice bath condition, generated hydrochloric acid gas is carried away by introducing nitrogen gas, and then the reaction is carried out for 2 to 4 hours at the temperature of 0 ℃. And (3) filtering the solid in the reaction system after the reaction is finished to obtain a filtrate, and removing the DCM solvent from the filtrate on a rotary evaporator to obtain a crude reaction product. The crude reaction product was distilled under reduced pressure to give a colorless liquid in 83% yield. Mass spectrum: 125.96. elemental analysis: c:18.99 percent; h:3.19 percent; cl:28.03 percent; o:25.30 percent; p:24.49 percent. The difference between the experimental value test and the theoretical value is less than 0.02 percent;
2) Synthesis of Compound a2
Adding the synthesized compound a1 into a 150mL single-neck round-bottom flask, adding 80mL anhydrous toluene, introducing oxygen, heating to 80 ℃ for reaction for 4-6h, removing the toluene solvent after the reaction is finished to obtain a reaction crude product, and finally distilling under reduced pressure to obtain the product with the yield of 74%. Mass spectrum: 141.96, elemental analysis: theoretical value C:16.86 percent; h:2.83 percent; cl:24.88 percent; o:33.69 percent; p:21.74 percent;
the difference between the experimental value test and the theoretical value is less than 0.02 percent.
3) Synthesis of Compound a3
5g of the compound a2 are dissolved in 20mL of THF, and 1.09eq of ethanol and 2eq of triethylamine (Et) are slowly added dropwise under ice-bath conditions 3 N), stirring and reacting for 4 hours at the temperature of 0 ℃, filtering to obtain filtrate after the reaction is finished, removing THF solvent of the reaction, and finally carrying out reduced pressure distillation to obtain a product, wherein the separation yield is 71%. Mass spectrum: 138.0, elemental analysis: theoretical value C:28.57 percent; h:5.40 percent; o:28.54 percent; p:18.42 percent; s:19.07%, and the difference between the experimental value test and the theoretical value is less than 0.02%;
4) Synthesis of Compound 1
Dissolving 5g of the compound a3 in 50mL of THF, slowly and dropwise adding 1.09eq of THF solution of N-fluoro-diphenyl sulfonamide (NFSI) under the ice bath condition, stirring and reacting for 2h under the ultraviolet irradiation of 365nm at the temperature of 0 ℃, then slowly returning to room temperature, filtering to obtain a filtrate after the reaction is finished, removing the THF solvent of the reaction, and finally carrying out reduced pressure distillation to obtain the product with the isolated yield of 58%.
The synthetic route of the above compound 1 is shown in fig. 1.
Mass spectrum, as shown in the spectrum of fig. 2: 155.99, elemental analysis: theoretical value C:25.81 percent; h:4.33 percent; f:10.21 percent; o:25.79 percent; p:16.64 percent; s:17.22 percent, and the difference between the experimental value test and the theoretical value is less than 0.02 percent, which indicates that the compound 1 product is obtained.
Example 2
Preparation of fluorinated cyclic phosphorus-containing molecular compound 2:
the preparation of compound 2 differs from the preparation of compound 1 in that step 4) the time of the fluorine substitution reaction with NFSI is doubled, and the amount of NFSI used is doubled, and the other steps are the same, and finally the product substituted by difluoride is isolated, the synthetic route is shown in fig. 3.
Example 3
Preparation of fluorinated cyclic phosphorus-containing molecular compound 3:
the preparation of compound 3 is similar to the preparation of compound a3 in steps 1) -3) of example 1, with the specific difference that the ethylene glycol in step 1) is replaced by trifluoromethyl ethylene glycol, ethanethiol is replaced by methanol, and the other steps are the same, and the synthetic route is shown in fig. 4.
Example 4
Preparation of fluorinated cyclic phosphorus-containing molecular compound 4:
the preparation of compound 4 was carried out in a similar manner to the preparation of compound 3 of example 3, except that the ethanethiol of step 3) was changed to trifluoromethylethanol, and the other steps were the same, and the synthetic route is shown in fig. 5.
Example 5
Preparation of fluorinated cyclic phosphorus-containing molecular compound 5:
the preparation of compound 5 is similar to the preparation of compound a3 in steps 1) to 3) of example 1, with the specific difference that ethanethiol in step 3) is changed to trifluoromethylthiol, and the other steps are the same, and the synthetic route is shown in fig. 6.
Example 6
Preparation of fluorinated cyclic phosphorus-containing molecular compound 6:
the preparation of compound 6 was carried out in a similar manner to the preparation of compound 3 of example 3, except that ethanethiol in step 3) was changed to trifluoromethylthiol, and the other steps were the same, and the synthetic route is shown in FIG. 7.
Example 7
Preparation of fluorinated cyclic phosphorus-containing molecular compound 7:
the preparation of compound 7 is similar to the preparation of compound a3 in steps 1) to 3) of example 1, with the specific difference that the ethylene glycol in step 1) is replaced by 1, 3-propanediol, the ethanethiol in step 3) is replaced by trifluoromethylethanol, and the other steps are the same, and the synthetic route is shown in fig. 8.
Example 8
Preparation of fluorinated cyclic phosphorus-containing molecular compound 8:
in the preparation of compound 8, the first three steps of the preparation of compounds h1 to h3 were the same as the first three steps of compound 7, and then h1 was carried out according to the procedure of example 1, step 4), wherein ethanethiol was replaced with methanol, and the synthetic route is shown in fig. 9.
Example 9
Preparation of fluorinated cyclic phosphorus-containing molecular compound 9:
the preparation of compound 9 was performed in a similar manner to the preparation of compound 3 in example 3, except that the trifluoromethyl glycol in step 1) was replaced by 2-trifluoromethyl-1, 3-propanediol, in which ethanethiol was replaced by methanol, and the other steps were the same, and the synthetic route was as shown in fig. 10.
Example 10
Preparation of fluorinated cyclic phosphorus-containing molecular compound 10:
the preparation of the compound j1, the compound j2 and the compound j3 is similar to the preparation of the compound 9, except that the 2-trifluoromethyl-1, 3-propanediol in the step 1) is replaced by 1, 3-dihydroxyacetone;
and compound 10 was prepared as:
5g of compound j3 was dissolved in 50mL of DCM, slowly added dropwise to a solution of 2.5eq diethylaminosulfur trifluoride (DAST) in DCM under ice-bath conditions, stirred at 0 ℃ for 24h, then slowly returned to room temperature, added to the ice-water mixture at the end of the reaction, followed by addition of 10% by weight of NaHCO 3 Stirring for 12h, separating and drying, removing the DCM solvent, and finally distilling under reduced pressure to obtain the product with the isolated yield of 67%. Mass spectrum: 188.00, elemental analysis: theoretical value C:25.55 percent; h:3.75 percent; f:20.20.17 percent; o:34.03 percent; p:16.47 percent, and the difference between the experimental value test and the theoretical value is less than 0.02 percent.
The synthetic route of compound 10 is shown in figure 11.
Example 11
Preparation of fluorinated cyclic phosphorus-containing molecular compound 11:
the preparation of compound 11 was carried out in a similar manner to the preparation of compound a3 of example 1, except that ethanethiol of step 3) was changed to 2, 2-trifluoroethyl-1-methanamine, and the other steps were the same, and the synthetic route is shown in FIG. 12.
Example 12
Preparation of fluorinated cyclic phosphorus-containing molecular compound 12:
the preparation of compound 12 was carried out in a similar manner to the preparation of compound 3 of example 3, except that ethanethiol of step 3) was changed to 2, 2-trifluoroethyl-1-methanamine, and the other steps were the same, and the synthetic route was as shown in FIG. 13.
Example 13
Preparation of fluorinated cyclic phosphorus-containing molecular compound 13:
the preparation of compound 13 was carried out in analogy to the preparation of compound 7 of example 7, with the specific difference that the 2, 2-trifluoroethanol of step 3) was changed to 2, 2-trifluoro-1-methyl-ethylamine, and the other steps were the same, and the synthetic route is shown in fig. 14.
Example 14
Preparation of fluorinated cyclic phosphorus-containing molecular compound 14:
the preparation of compound 14 was carried out in a similar manner to the preparation of compound 9 of example 9, except that 2-trifluoromethyl-1, 3-propanediol from step 3) was changed to 2, 2-trifluoromethyl-ethylamine, and the other steps were the same, and the synthetic route was as shown in fig. 15.
Example 15
Preparation of fluorinated cyclic phosphorus-containing molecular compound 32:
preparation of compound 32 was carried out in a similar manner to the preparation of compound 9 of example 9, except that 2-trifluoromethyl-1, 3-propanediol in step 3) was replaced by N, N-dimethyl-2-trifluoromethyl-ethylenediamine, and the other steps were the same, the synthetic route being shown in fig. 16.
Example 16
Preparation of fluorinated cyclic phosphorus-containing molecular compound 33:
the preparation of compound 33 was carried out in a similar manner to the preparation of compound 7 of example 7, except that 1, 3-propanediol in step 1) was replaced by N, N-dimethylethylenediamine, and the other steps were the same, the synthetic route being shown in FIG. 17.
The solvent formed by the fluorinated cyclic phosphorus-containing molecules synthesized in the examples and the common lithium salt LiFSI are prepared into 1M lithium ion battery electrolyte to be used in the following batteries, and electrochemical performance tests are carried out:
preparing a graphite electrode: graphite, acetylene black, PVDF binder were mixed at a ratio of 87 2 The electrode wafer is put into a glove box for standby;
preparation of NCM111 electrode: NCM111, acetylene black, PVDF binder were mixed at a ratio of 80 2 The electrode wafer is put into a glove box for standby;
and in a glove box, the prepared pole piece is taken as a positive electrode, a lithium piece is taken as a negative electrode, and the Ceglad 2400 is taken as a diaphragm to assemble the battery. The electrochemical performance of the graphite | Li battery is tested at room temperature by assembling the graphite | Li battery by using commercial electrolyte and electrolyte prepared from fluorinated cyclic phosphorus-containing molecules of the invention as electrolyte.
The electrochemical performance of the battery obtained above was tested, and the test results were as follows:
as shown in FIG. 18, the graphite | Li cell was used in a commercial electrolyte (1M LiPF) 6 in EC: DMC) and compound 1 (1M LiFSI) in electrolyte. As can be seen from the figure, the specific capacity retention rate of the battery using the electrolyte of 1M LiFSI compound 1 is 95% or more after 100 cycles, which is higher than that of the commercial electrolyte of 93%. Furthermore, the graphite electrode material exhibits very excellent cycle stability, the average coulombic efficiency of which is excellent in the electrolytic solution containing the fluorinated cyclic phosphorus-containing molecule of the present invention with the compound 1The rate reaches 99.8 percent. The good film-forming property of the electrolyte containing the fluorinated cyclic phosphorus-containing molecule is fully demonstrated, so that the graphite Li battery has good cycle performance;
as shown in FIG. 19, the NCM111| Li cell was used in a commercial electrolyte (1M LiPF) 6 DMC) and compound 1, and the battery using the electrolyte (1M LiFSI) prepared by the compound 1 shows better cycle performance, and meanwhile, the average coulombic efficiency of the battery reaches 99.5 percent, so that the battery can be popularized and applied to the research of high-safety and long-cycle batteries.

Claims (2)

1. A fluorocyclic phosphorus-containing molecule comprising one of the following molecular structures:
Figure FDA0004102656970000011
Figure FDA0004102656970000021
2. a fluorinated cyclic phosphorus-containing molecule according to claim 1 for use as an electrolyte or additive in a lithium-ion or sodium-ion or potassium-ion secondary battery.
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