CN116143836A - Phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, preparation method and application of phosphorus-containing nitrogen-fluorine flame-retardant electrolyte in lithium battery - Google Patents
Phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, preparation method and application of phosphorus-containing nitrogen-fluorine flame-retardant electrolyte in lithium battery Download PDFInfo
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- CN116143836A CN116143836A CN202310079046.6A CN202310079046A CN116143836A CN 116143836 A CN116143836 A CN 116143836A CN 202310079046 A CN202310079046 A CN 202310079046A CN 116143836 A CN116143836 A CN 116143836A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000003063 flame retardant Substances 0.000 title claims abstract description 90
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 82
- 239000011574 phosphorus Substances 0.000 title claims abstract description 82
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003792 electrolyte Substances 0.000 title claims abstract description 63
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 239000013067 intermediate product Substances 0.000 claims abstract description 10
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000004985 diamines Chemical class 0.000 claims abstract description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000003791 organic solvent mixture Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 5
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 3
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000654 additive Substances 0.000 abstract description 13
- 230000000996 additive effect Effects 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000006683 Mannich reaction Methods 0.000 abstract description 3
- 238000007033 dehydrochlorination reaction Methods 0.000 abstract description 3
- 239000005457 ice water Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 5
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- SASGRYXPUKWRAZ-UHFFFAOYSA-N [N].[P].[F] Chemical compound [N].[P].[F] SASGRYXPUKWRAZ-UHFFFAOYSA-N 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- PMPYSSMGWFNAAQ-UHFFFAOYSA-N dichloromethane;n,n-diethylethanamine Chemical compound ClCCl.CCN(CC)CC PMPYSSMGWFNAAQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6509—Six-membered rings
- C07F9/650952—Six-membered rings having the nitrogen atoms in the positions 1 and 4
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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
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Abstract
The invention provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, a preparation method, a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte and application thereof in a lithium battery, wherein the preparation method of the additive comprises the following steps: dehydrochlorination reaction is carried out on phosphorus trichloride and trifluoroalcohol in ice-water bath to obtain an intermediate product; and then the intermediate product is subjected to Mannich reaction with formaldehyde and diamine, and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive is obtained after purification. The flame-retardant electrolyte additive has good affinity with the mixture of lithium salt and organic solvent, and meanwhile, has synergistic flame-retardant effect among phosphorus, nitrogen and fluorine, so that the safety performance of the electrolyte can be greatly improved under the condition that the conductivity, viscosity and the like of the electrolyte are not influenced. In addition, the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive can achieve the effects of self-extinguishment and even incombustibility under the condition of small addition amount, and has wide application prospects in the fields of electric energy storage, electric automobiles and the like.
Description
Technical Field
The invention relates to the technical field of energy sources and new materials, in particular to a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, a preparation method, a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte and application thereof in lithium batteries.
Background
Lithium batteries have become one of the important energy storage devices. The method is widely applied to the fields of electric energy storage power supplies, mobile communication, military equipment, aerospace and the like, and has very broad application prospects in electric energy storage, electric automobiles and the like. However, the characteristics of high working voltage, high energy density and the like endow the lithium battery with better electrochemical performance, and meanwhile, the lithium battery is also provided with serious potential safety hazard.
At present, commercial lithium ion battery electrolyte mainly comprises inflammable liquid organic matters such as ethylene carbonate, diethyl carbonate, methyl ethyl carbonate and the like, and the flash point and the boiling point of the electrolyte are low, so that the battery can possibly bulge, and even serious safety accidents occur. Because of the large amount of inflammable materials (such as liquid ester electrolyte) used in lithium batteries, once the batteries are out of control, the internal pressure exceeds the bearable range, and the electrolyte steam which is inflammable at extremely high temperature is ejected, so that rapid combustion and even explosion are caused. In recent years, the combustion and explosion accidents of lithium batteries greatly threaten personal and property safety. Therefore, the introduction of the flame-retardant electrolyte additive with higher flash point and boiling point into the electrolyte is of great significance for effectively improving the safety performance of the electrolyte.
Disclosure of Invention
The invention aims to provide a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive which has higher flash point and boiling point and better compatibility with a mixture of lithium salt and an organic solvent.
The invention further aims to provide a preparation method of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, which is characterized in that after dehydrochlorination reaction is carried out on phosphorus trichloride and trifluoroalcohol, the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive is subjected to Mannich reaction with formaldehyde and diamine, and finally the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive is obtained.
The third purpose of the invention is to provide the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte which has better safety performance.
The fourth object of the invention is to provide a preparation method of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which is simple to operate and controllable in parameters, and is suitable for industrial mass production.
The fifth object of the invention is to provide the application of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte in the preparation of lithium ion batteries.
The invention solves the technical problems by adopting the following technical scheme.
The invention provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, which has the structural formula:
wherein R1 is any one of the following groups: -CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -; r2 is any one of the following groups: -CH 2 -CH 2 -,-CH(CH 3 )-CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -; r3 is any one of the following groups: -CH 2 -，-CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -。
The invention provides a preparation method of a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, which comprises the following steps:
s1, dissolving phosphorus trichloride in a first solvent, cooling to 0-5 ℃, dropwise adding tertiary butanol, stirring for 50-70 min, then dropwise adding trifluoroalcohol to react for 12-16 h, heating for reflux, and distilling under reduced pressure to obtain an intermediate product;
s2, after the intermediate product, formaldehyde and diamine react in a second solvent, purifying to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive.
The invention provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which comprises a lithium salt, an organic solvent mixture and a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive.
The invention provides a preparation method of a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which comprises the following steps:
and mixing and stirring the lithium salt, the organic solvent mixture and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive for 1-10 hours to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte.
The invention provides application of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte in preparation of lithium ion batteries.
The phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, the preparation method and the application thereof in the lithium battery have the beneficial effects that:
1. the structure of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive contains a large amount of flame-retardant elements such as phosphorus, nitrogen, fluorine and the like, and can play a good role in synergistic flame retardance. The additive can obviously improve the safety performance of the electrolyte of the lithium battery under the condition of not affecting the conductivity, viscosity and the like of the electrolyte, so that the additive has wide application prospect in the fields of electric energy storage, electric automobiles and the like.
2. The phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive has higher flash point and boiling point, and has good compatibility with a lithium salt and organic solvent mixture in the electrolyte. The electrolyte with better safety performance can be prepared by mixing the electrolyte with a mixture of lithium salt and an organic solvent. The electrolyte is used in the lithium battery, so that the risk of explosion of the lithium battery can be reduced.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the phosphorus-containing nitrogen-fluorine flame retardant electrolyte additive of example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance fluorine spectrum of the phosphorus-nitrogen-fluorine-containing flame retardant electrolyte additive of example 1 of the present invention;
FIG. 3 is a flow chart of the preparation of the additive for the flame retardant electrolyte containing phosphorus, nitrogen and fluorine.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, the preparation method and the application thereof in lithium batteries are specifically described below.
The embodiment of the invention provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, which has the structural formula:
wherein R1 is any one of the following groups: -CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -; r2 is any one of the following groups: -CH 2 -CH 2 -,-CH(CH 3 )-CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -; r3 is any one of the following groups: -CH 2 -，-CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -。
The structure of the additive for the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte contains a large amount of flame-retardant elements such as phosphorus, nitrogen, fluorine and the like. The compound containing phosphorus, nitrogen, fluorine and other flame retardant elements has obvious flame retardant effect of condensed phase and gas phase, and is decomposed into free radicals at high temperature or catalyzed and combustible materials are cracked into carbon, thereby playing a role in blocking combustion. By introducing fluorine element into the structure, the structure has better synergistic flame retardant effect, so that the flame retardant efficiency of the prepared electrolyte is further improved. In addition, the electrolyte can achieve the effect of self-extinguishment and even incombustibility under the condition of less consumption of the flame retardant additive.
Referring to fig. 3, the invention provides a preparation method of a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive, which comprises the following steps:
s1, dissolving phosphorus trichloride in a first solvent, cooling to 0-5 ℃, dropwise adding tertiary butanol, stirring for 50-70 min, then dropwise adding trifluoroalcohol for reacting for 12-16 h, heating for reflux, and distilling under reduced pressure to obtain an intermediate product. Preferably, in the present invention, the dropping of t-butanol is performed using a constant pressure dropping funnel, and stirred in an ice bath after the dropping, and then the trifluoroalcohol is dropped using a constant pressure dropping funnel and reacted in an ice water bath. After the reaction was completed, reflux was performed for 3 hours to remove the excess hydrogen chloride gas in the solution, and the residual solvent was removed by distillation under reduced pressure to obtain an intermediate product.
Further, in a preferred embodiment of the present invention, the first solvent is selected from one of acetone, butanone, dichloromethane, chloroform, dioxane, and tetrahydrofuran.
Further, in a preferred embodiment of the present invention, the molar ratio of the phosphorus trichloride, the tertiary butanol and the trifluoroalcohol is 1:0.8 to 1.2: 1.8-2.2, wherein the trifluoroalcohol is selected from one of trifluoroethanol, 3-trifluoropropanol and 4, 4-trifluorobutanol, and the dropwise adding time of the trifluoroalcohol is 0.5-1 h.
S2, after the intermediate product, formaldehyde and diamine react in a second solvent, purifying to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive.
Further, in a preferred embodiment of the present invention, the second solvent is selected from one of tetrahydrofuran solution of hydrochloric acid, dichloromethane solution of hydrochloric acid, tetrahydrofuran solution of triethylamine, dichloromethane solution of triethylamine, the formaldehyde is selected from one of trioxymethylene, paraformaldehyde and aqueous formaldehyde solution, and the diamine is selected from one of piperazine, ethylenediamine, 1, 2-propylenediamine, butylenediamine and hexamethylenediamine. Preferably, when the second solvent is an acidic solution, its pH is around 5; when the second solvent is an alkaline solution, the pH value is about 9.
Further, in the preferred embodiment of the invention, the reaction temperature is 30-60 ℃ and the reaction time is 4-12 h.
The synthetic route of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive (formula I) is shown as follows:
wherein R1 is any one of the following groups: -CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -; r2 is any one of the following groups: -CH 2 -CH 2 -,-CH(CH 3 )-CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -。
The invention firstly carries out dehydrochlorination reaction through phosphorus trichloride and trifluoro alcohol, then carries out Mannich reaction with formaldehyde and diamine, and finally obtains the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive. The phosphorus, nitrogen and fluorine in the additive structure have good synergistic effect, and the additive has good compatibility with the mixture of lithium salt and organic solvent, so that the defects of poor compatibility, low flame retardant efficiency and the like of electrolyte additives in an electrolyte system are overcome, and technical support is provided for improving the safety performance of the electrolyte of the lithium battery.
The invention provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which comprises a lithium salt, an organic solvent mixture and a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive.
The invention provides a preparation method of a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which comprises the following steps:
and mixing and stirring the lithium salt, the organic solvent mixture and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive for 1-10 hours to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte.
In a preferred embodiment, the mass percentage of the additive of the phosphorus-nitrogen-fluorine-containing flame-retardant electrolyte is 5-30wt%; the concentration of lithium hexafluorophosphate is 0.5-1.0 mol/L.
Further, in a preferred embodiment of the present invention, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate, and lithium bistrifluoromethylsulfonylimide, and the organic solvent mixture is a carbonate organic solvent mixture. Preferably, the organic solvent mixture is a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DMC), and the volume ratio of EC to DMC in the EC/DMC mixed solution is 1:1.
The invention also provides application of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte in preparing lithium ion batteries.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive provided by the embodiment is prepared according to the following method:
1mol of phosphorus trichloride and 200mL of methylene chloride were added to a 500mL flask, cooled to 0℃with an ice bath, and 100mL of a methylene chloride solution of 0.01mol/mL of t-butanol was slowly added dropwise with a constant pressure dropping funnel, over about 45 minutes. Stirring was carried out for one hour in an ice bath, and 100mL of a 0.02mol/mL dichloromethane solution of trifluoroethanol was then slowly added dropwise with a constant pressure dropping funnel over about 30 minutes. After the completion of the dropping, the reaction was carried out for 12 hours with stirring. The solution was then heated to 47 ℃ and refluxed for three hours to remove hydrogen chloride, and then dichloromethane was removed by rotary evaporation to obtain an intermediate product. Then adding 1mol of paraformaldehyde, 0.5mol of piperazine and a certain amount of triethylamine methylene dichloride solution to enable the pH value of the solution to be 8.5-9, reacting for 4 hours at 70 ℃, and purifying to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive (TFPFP).
The synthetic route and the molecular structural formula of the target product TFPFP are shown as follows:
example 2
The embodiment provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which is prepared according to the following method:
uniformly mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:1 to obtain an organic solvent mixture, adding lithium hexafluorophosphate (1M) and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive of the embodiment 1, and fully stirring for 1h to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte (LiPF 6 EC/DMC/TFPFP). Wherein, in the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, the mass percentage of the TFPFP is 5wt%.
Example 3
The embodiment provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which is prepared according to the following method:
uniformly mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:1 to obtain an organic solvent mixture, then adding lithium hexafluorophosphate (1M) and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive of the embodiment 1, and fully stirring for 1h to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte (LiPF 6/EC/DMC/TFPFP). Wherein, in the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, the mass percentage of the TFPFP is 10wt%.
Example 4
The embodiment provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which is prepared according to the following method:
uniformly mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:1 to obtain an organic solvent mixture, adding lithium hexafluorophosphate (1M) and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive of the embodiment 1, and fully stirring for 1h to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte (LiPF 6 EC/DMC/TFPFP). Wherein, the phosphorus-containing nitrogen-fluorine resistorIn the fuel electrolyte, the mass percentage of TFPFP is 20wt%.
Example 5
The embodiment provides a phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, which is prepared according to the following method:
uniformly mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:1 to obtain an organic solvent mixture, adding lithium hexafluorophosphate (1M) and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive of the embodiment 1, and fully stirring for 1h to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte (LiPF 6 EC/DMC/TFPFP). Wherein, in the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte, the mass percentage of the TFPFP is 30wt%.
Comparative example 1
This comparative example provides an electrolyte prepared according to the following method:
uniformly mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:1 to obtain an organic solvent mixture, then adding lithium hexafluorophosphate (1M), and fully stirring for 1h to obtain an electrolyte (LiPF) 6 /EC/DMC)。
Comparative example 2
This comparative example provides an electrolyte prepared according to the following method:
uniformly mixing ethylene carbonate and dimethyl carbonate according to a volume ratio of 1:1 to obtain an organic solvent mixture, adding lithium hexafluorophosphate (1M) and hexamethylphosphoric triamide (HMPA) serving as a traditional additive, and fully stirring for 1h to obtain an electrolyte (LiPF) 6 EC/DMC/HMPA). Wherein, in the electrolyte, the mass percent of HMPA is 5wt%.
Test example 1
The test example adopts 1 H NMR 19 F NMR structural characterization was performed on the phosphorus-nitrogen-fluorine-containing flame retardant electrolyte additive solution of example 1.
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of the additive solution of the phosphorus-containing nitrogen-fluorine flame retardant electrolyte of example 1. FIG. 2 shows the nuclear magnetic resonance fluorine spectrum of the additive solution of the phosphorus-containing nitrogen-fluorine flame retardant electrolyte in example 1. As can be seen from FIG. 1, the peak around 4.55ppm is derived from CF 3 CH 2 The peak around 3ppm of hydrogen atoms in-O is attributed toO＝P-CH 2 The characteristic peak of 2.65ppm of hydrogen atoms in N is derived from piperazine, and the ratio of the integral area of the graph is 2:1:2, and the ratio of the number of the hydrogen atoms in the structural formula is 8:4:8.
As can be seen from fig. 2, only one characteristic peak is found in the figure. The results of both fig. 1 and fig. 2 demonstrate successful preparation of the final product TFPFP.
Test example 2
This test example was conducted on the phosphorus-containing nitrogen-fluorine flame retardant electrolytes of examples 2 to 5 and the electrolytes of comparative examples 1 and 2, respectively. The results of the combustion test are shown in Table 1.
TABLE 1 Combustion test of phosphorus-containing Nitrogen-fluorine flame retardant electrolyte
As can be seen from Table 1, the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive prepared by the invention has excellent self-extinguishing performance and safety performance compared with the traditional additive hexamethylphosphoric triamide.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive is characterized by comprising the following structural formula:
wherein R1 is any one of the following groups: -CH 2 -、-CH 2 -CH 2 -、-CH 2 -CH 2 -CH 2 -; r2 is any one of the following groups: -CH 2 -CH 2 -、-CH(CH 3 )-CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -; r3 is any one of the following groups: -CH 2 -，-CH 2 -CH 2 -，-CH 2 -CH 2 -CH 2 -。
2. The method for preparing the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive according to claim 1, which comprises the following steps:
s1, dissolving phosphorus trichloride in a first solvent, cooling to 0-5 ℃, dropwise adding tertiary butanol, stirring for 50-70 min, then dropwise adding trifluoroalcohol to react for 12-16 h, heating for reflux, and distilling under reduced pressure to obtain an intermediate product;
s2, after the intermediate product, formaldehyde and diamine react in a second solvent, purifying to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive.
3. The method according to claim 2, wherein in step S1, the first solvent is selected from one of acetone, butanone, dichloromethane, chloroform, dioxane, and tetrahydrofuran.
4. The method according to claim 2, wherein in step S1, the molar ratio of phosphorus trichloride, t-butanol and trifluoroalcohol is 1:0.8 to 1.2: 1.8-2.2, wherein the trifluoroalcohol is selected from one of trifluoroethanol, 3-trifluoropropanol and 4, 4-trifluorobutanol, and the dropwise adding time of the trifluoroalcohol is 0.5-1 h.
5. The method according to claim 2, wherein in step S2, the second solvent is selected from one of tetrahydrofuran solution of hydrochloric acid, dichloromethane solution of hydrochloric acid, tetrahydrofuran solution of triethylamine, dichloromethane solution of triethylamine, formaldehyde is selected from one of trioxymethylene, paraformaldehyde and aqueous formaldehyde solution, and diamine is selected from one of piperazine, ethylenediamine, 1, 2-propylenediamine, butylenediamine, hexamethylenediamine.
6. The preparation method according to claim 2, wherein in the step S2, the reaction temperature is 30 to 60 ℃ and the reaction time is 4 to 12 hours.
7. A phosphorus-containing nitrogen-fluorine flame-retardant electrolyte comprising a lithium salt, an organic solvent mixture, and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive of claim 1.
8. The phosphorus-containing nitrogen-fluorine flame-retardant electrolyte according to claim 7, wherein the lithium salt is one or more selected from lithium hexafluorophosphate, lithium difluorooxalato borate, lithium difluorodioxaato phosphate and lithium bistrifluoromethylsulfonylimide, and the organic solvent mixture is a carbonate organic solvent mixture.
9. A method for preparing the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte according to any one of claims 7 or 8, comprising the following steps:
and mixing and stirring the lithium salt, the organic solvent mixture and the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte additive for 1-10 hours to obtain the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte.
10. Use of the phosphorus-containing nitrogen-fluorine flame-retardant electrolyte according to any one of claims 7 or 8 in the preparation of lithium ion batteries.
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