CN117326978A - Synthesis method and application of 2, 3-dicyanohydroquinone derivative - Google Patents
Synthesis method and application of 2, 3-dicyanohydroquinone derivative Download PDFInfo
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- CN117326978A CN117326978A CN202311251857.6A CN202311251857A CN117326978A CN 117326978 A CN117326978 A CN 117326978A CN 202311251857 A CN202311251857 A CN 202311251857A CN 117326978 A CN117326978 A CN 117326978A
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- dicyanohydroquinone
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- MPAIWVOBMLSHQA-UHFFFAOYSA-N 3,6-dihydroxybenzene-1,2-dicarbonitrile Chemical class OC1=CC=C(O)C(C#N)=C1C#N MPAIWVOBMLSHQA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 7
- 150000001336 alkenes Chemical class 0.000 claims abstract description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 2
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000005336 allyloxy group Chemical group 0.000 description 6
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 6
- 229920006391 phthalonitrile polymer Polymers 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- -1 lithium hexafluorophosphate Chemical group 0.000 description 5
- 239000002000 Electrolyte additive Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 230000003442 weekly effect Effects 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WSIDFIREQDHYPW-UHFFFAOYSA-N 4-bromo-1,1-difluorobut-1-ene Chemical compound FC(F)=CCCBr WSIDFIREQDHYPW-UHFFFAOYSA-N 0.000 description 1
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 1
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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 synthesis method and application of a 2, 3-dicyanohydroquinone derivative, wherein the compound takes 2, 3-dicyanohydroquinone as a starting material of reaction, and the target product is obtained through nucleophilic substitution reaction with halogenated alkene or alkyne. The 2, 3-dicyanohydroquinone derivative has the structure that the benzene ring is connected with the alkene unsaturated alkoxy and the cyano, can effectively form a stable SEI film when being applied to a lithium ion battery in charge and discharge, and the cyano can possibly form a relatively effective protective film on the surface of the positive electrode in the charge and discharge process of the battery to cover the active site of the battery, so that the reactivity of the positive electrode to electrolyte can be reduced, and the reaction between the positive electrode and HF acid can be carried out at high temperature to reduce the damage of the HF acid to the surface of the electrode and the current collector, thereby improving the high-low temperature performance and the cycle performance of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion battery electrolyte, in particular to a synthesis method and application of a 2, 3-dicyanohydroquinone derivative.
Background
The lithium ion battery has the advantages of no memory effect, environmental friendliness, high energy density and the like, and is widely applied to portable electronic equipment such as notebook computers, mobile phones, cameras and the like, so that great convenience is brought to life of people. However, there are many aspects of the lithium ion battery that need improvement, such as the cycle stability and high-low temperature performance of the battery, which are one of the important factors that restrict the large-scale application of the lithium ion battery in electric vehicles. The electrolyte is one of key materials of the lithium ion battery, directly determines the cycle stability and high-low temperature performance of the battery, and the performance of the battery is generally improved by changing the components of the electrolyte at present.
In order to solve the current problems, the invention uses the 2, 3-dicyanohydroquinone derivative as the lithium ion electrolyte additive to be applied to the lithium ion battery, wherein the benzene ring of the structure is connected with the alkene unsaturated alkoxy and cyano, a stable SEI film can be effectively formed during charge and discharge, and the cyano forms a relatively effective protective film on the surface of the positive electrode in the process of charge and discharge of the battery to cover the active site of the positive electrode, so that the reactivity of the positive electrode to the electrolyte can be reduced, the positive electrode can react with HF acid at high temperature, the damage of the HF acid to the surface of the electrode and the current collector is reduced, and the high-low temperature performance and the cycle performance of the battery are improved.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provide a synthesis method of a 2, 3-dicyanohydroquinone derivative and application of the 2, 3-dicyanohydroquinone derivative as an additive in lithium ion battery electrolyte.
The technical scheme adopted by the invention is as follows:
a derivative having the structural formula:
wherein R is 1 ，R 2 Is a straight chain, branched chain alkene or alkyne containing from 2 to 6 carbon atoms;
preferably, the structural formula of the derivative comprises any one of the following structures:
the synthesis method of the 2, 3-dicyanohydroquinone derivative comprises the following steps:
under the protection of nitrogen, taking raw material 2, 3-dicyanohydroquinone and halogenated alkene or alkyne to carry out nucleophilic substitution reaction to obtain 2, 3-dicyanohydroquinone derivative, wherein the reaction is as follows:
wherein X is a halogen atom;
further, 2, 3-dicyanohydroquinone and R as described in the synthesis reaction 1 The molar ratio of X is 1:1 to 1.2.
Further, 2, 3-dicyanohydroquinone and the method for synthesizing the sameR 2 The molar ratio of X is 1:1 to 1.2.
Further, the reaction temperature in the synthesis reaction is-10℃to 100℃and preferably-5℃to 70 ℃.
Further, the synthesis reaction time is 2 to 24 hours, preferably 8 to 16 hours.
Further, in the synthesis reaction, the reaction solvent is aprotic polar solvents such as N, N-dimethylformamide, acetone, acetonitrile, dimethyl sulfoxide and the like; the base used in the reaction is an inorganic base such as potassium carbonate, sodium bicarbonate, or an organic base such as triethylamine, isopropylamine, diisopropylamine, pyridine, or the like.
Further, the crude product obtained after the reaction is crystallized and purified to obtain the target product 2, 3-dicyanohydroquinone derivative.
A lithium ion battery electrolyte comprising a lithium salt, an organic solvent and an additive, wherein the additive comprises the 2, 3-dicyanohydroquinone derivative and fluoroethylene carbonate; the mass percentage of the 2, 3-dicyano hydroquinone derivative is 0-1.5wt%, and the mass percentage of the fluoroethylene carbonate is 0-4.0wt%.
The lithium salt is lithium hexafluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, tris (trifluoromethylsulfonyl) methyllithium, bis (trifluoromethylsulfonyl) methyllithium, lithium trifluoromethylsulfonate, lithium bistrifluoromethylsulfonimide, lithium bisfluorosulfonimide, liAsF 6 、LiClO 4 Mixing one or more of the above materials according to any proportion, preferably, the lithium salt is lithium hexafluorophosphate; the mass percentage of the lithium salt is 12.50%.
The organic solvent is one or more of ethylene carbonate, fluoroethylene carbonate, propylene carbonate, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, ethyl acetate, vinylene carbonate, propylene sulfite, vinyl sulfate, propylene sultone, lithium difluorophosphate and triphenyl phosphite which are mixed according to any proportion; preferably, the organic solvent combination is: the mass percentage of the organic solvent is 82% -87.5%.
The invention provides a synthesis method and application of a 2, 3-dicyanohydroquinone derivative, wherein the synthesis method has the advantages of low cost and easily obtained synthesis raw materials and simpler synthesis process. The 2, 3-dicyanohydroquinone derivative has the advantages that the benzene ring of the structure is connected with the alkene unsaturated alkoxy and the cyano, the stable SEI film can be effectively formed when the SEI film is applied to a lithium ion battery in charge and discharge, and the cyano can possibly form a relatively effective protective film on the surface of the positive electrode in the charge and discharge process of the battery to cover the active site of the SEI film, so that the reactivity of the positive electrode to electrolyte can be reduced, and the SEI film can react with HF acid at high temperature to reduce the damage of the HF acid to the surface of the electrode and the current collector, so that the high-low temperature performance and the cycle performance of the battery are improved.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 3, 6-bis (allyloxy) phthalonitrile in example 1.
Detailed Description
The invention is further described below in connection with the examples, which are not to be construed as limiting the invention in any way, but rather as a limited number of modifications which are within the scope of the appended claims.
In order to explain the technical content of the present invention in detail, the following description will further explain the embodiments.
The structure of the 2, 3-dicyanohydroquinone derivative in each embodiment of the invention is as follows:wherein R is 1 ，R 2 In the examples, which are straight-chain, branched-chain alkenes or alkynes having 2 to 6 carbon atoms, the following specific structures are illustrated:
example 1
The structural formula of 3, 6-bis (allyloxy) phthalonitrile is as follows:
the synthesis steps are as follows:
150ml of DMF,20.0g (124.9 mmol) of 2, 3-dicyanohydroquinone, 34.5g (249.6 mmol) of potassium carbonate and nitrogen are placed in a three-port reaction bottle, the reaction solution is cooled to-5 ℃ under nitrogen atmosphere, 31.6g (261.2 mmol) of allyl bromide is added dropwise, the reaction is carried out for 30 minutes after the dropwise addition, the temperature is raised to 100 ℃ for reaction for 8 hours, the reaction solution is cooled to room temperature, the reaction solution is slowly poured into 300ml of water and filtered, the filter cake is washed with 50ml of water for three times, a crude product is obtained after drying, and 26.0g (108.2 mmol) of a target product is obtained after the crude product is recrystallized and purified by ethyl acetate, and the yield is 86.6%.
Examples 2 to 6
As with the reaction procedure of example 1, the specific products and reaction conditions are identified in Table 1.
TABLE 1 Structure of the products and the respective reaction conditions and yields corresponding to examples 2-6
Example 7
The synthetic product of this example was 3, 6-bis ((4, 4-difluorobut-3-en-1-yl) oxy) phthalonitrile having the following structure:
the synthesis steps are as follows:
150ml of DMF,20.0g (124.9 mmol) of 2, 3-dicyanohydroquinone, 34.5g (249.6 mmol) of potassium carbonate and nitrogen are placed in a three-port reaction bottle, the reaction solution is cooled to-10 ℃ under nitrogen atmosphere and then 44.7g (261.6 mmol) of 4-bromo-1, 1-difluorobutene are added dropwise, the reaction is carried out for 30 minutes after the dropwise addition, the temperature is raised to 70 ℃ for 24 hours, the reaction solution is cooled to room temperature and then slowly poured into 300ml of water, the filtration is carried out, the filter cake is washed with 50ml of water for three times, a crude product is obtained after drying, and 33.2g (97.6 mmol) of the target product is obtained after crystallization and purification of ethyl acetate, and the yield is 78.1%.
Example 8
The synthetic product of this example was 3- (allyloxy) -6- (but-3-en-1-yloxy) phthalonitrile, which had the following structure:
the synthesis steps are as follows:
150ml of DMF,20.0g (124.9 mmol) of 2, 3-dicyanohydroquinone, 34.5g (249.6 mmol) of potassium carbonate and nitrogen are replaced three times in a three-port reaction bottle, 15.1g (124.9 mmol) of allyl bromide is dropwise added after the reaction solution is cooled to-5 ℃ under nitrogen atmosphere, the dropwise addition is completed, the reaction is kept for 2 hours, 18.5g (137.4 mmol) of 4-bromo-1-butene is continuously dropwise added, the reaction is kept for 30 minutes, then the reaction is slowly warmed to 70 ℃ for 16 hours, after the reaction solution is cooled to room temperature, the reaction solution is slowly poured into 300ml of water and filtered, the filter cake is washed three times by 50ml of water, the crude product is obtained after the drying, and 21.6g (84.9 mmol) of the target product is obtained after the purification by crystallization of ethyl acetate, and the yield is 68.0%.
Examples 9 to 14
As with the reaction procedure of example 8, the specific synthetic products and reaction conditions are identified in Table 2:
TABLE 2 Structure of the products and the respective reaction conditions and yields corresponding to examples 9-14
The 2, 3-dicyanohydroquinone derivatives prepared in each example were subjected to nuclear magnetic resonance spectroscopy, as shown in FIG. 1, which shows the nuclear magnetic resonance spectrum of 3, 6-bis (allyloxy) phthalonitrile prepared in example 1. 1HNMR: δ4.62 (4H, d, J=7.5 Hz), 5.30-5.50 (4H, 5.32 (dd, J=16.5, 1.3 Hz), 5.48 (dd, J=10.7, 1.3 Hz)), 6.00 (2H, ddt, J=16.5, 10.7,7.5 Hz), 7.25 (2H, d, J=8.5 Hz).
Application examples 1 to 17
The preparation of the electrolyte was performed using the 2, 3-dicyanohydroquinone derivative prepared in each of the above examples as one of the electrolyte additives. The process of electrolyte configuration is as follows:
under the closed environment condition that the water content is less than or equal to 10ppm, the electrolyte consists of the following components in percentage by mass based on the total weight of the electrolyte: mixing 82-87.5wt% of organic solvent (ethylene carbonate/methyl ethyl carbonate/diethyl carbonate according to the mass ratio of about 1:1:1), adding 12.50wt% of lithium hexafluorophosphate, stirring and dissolving, and finally adding 0-1.50wt% of one of the 2, 3-dicyanohydroquinone derivatives prepared in examples 1-14 and 0-4wt% of fluoroethylene carbonate as electrolyte additives, and stirring uniformly to obtain different lithium ion battery electrolytes.
Comparative examples 1 to 2 were used
The electrolyte prepared in comparative example was used without adding the 2, 3-dicyanohydroquinone derivative of the present invention.
The components and contents of the electrolyte for each application example configuration are shown in table 3 below:
TABLE 3 electrolyte Components and content corresponding to examples 15-31 and comparative examples 1-2
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Preparation of cell
The battery core adopts a lithium cobalt oxide graphite system, and the formula of the positive electrode comprises: lithium cobaltate LC109RH: SP: pvdf=96.5: 2:1.5; the formula of the negative electrode comprises the following steps: artificial graphite S360: SP: CMC2200: LA136 d=96.5: 1:0.5:2; the diaphragm adopts a PE diaphragm with the thickness of 20 mu m, the negative current collector adopts a copper foil with the thickness of 10 mu m, the positive current collector adopts an aluminum foil with the thickness of 14 mu m, the nominal capacity of the designed battery is 1050mAh, and the N/P ratio of the positive electrode and the negative electrode is controlled to be 1.08.
Test part
The electrolytes prepared in comparative examples 1 to 2 and examples 1 to 17 were injected into the above-prepared batteries, and the batteries were tested for cycle performance, high-low temperature discharge performance, and high-temperature storage performance, corresponding to battery numbers 1# -19# respectively, and the test results are shown in table 4.
The high temperature storage test steps are as follows: charging at 25 ℃ with 0.33C current and constant voltage until the limiting voltage reaches 4.4V, ending the charging when the cut-off current is reduced to 0.02C, and ending the discharging when the constant current of 0.33C discharges to the cut-off voltage of 3.0V, wherein the initial capacity is the initial capacity; charging with 0.33C current, constant current and constant voltage until the limiting voltage reaches 4.4V, ending the charging when the cut-off current is reduced to 0.02C, and measuring and recording the voltage and the internal resistance of the battery cell after ending; placing the sample in an open circuit at 60+/-2 ℃ for 7 days; taking out the sample, standing at room temperature for 5 hours, observing the appearance of the sample, and measuring and recording the voltage and internal resistance of the sample; the discharge is ended when the constant current discharge reaches the cut-off voltage of 3.0V at 25 ℃ with the current of 0.33C, and the discharge capacity is recorded; the method comprises the steps of charging at a constant current and constant voltage with a current of 0.33C until the limiting voltage reaches 4.4V, ending the charging when the cut-off current is reduced to 0.02C, ending the discharging when the constant current is discharged to a cut-off voltage of 3.0V with a current of 0.33C, ending the discharging after 3 weeks of circulation, recording the highest primary discharge capacity, and calculating the internal resistance change rate before and after high-temperature storage, the capacity retention rate after high-temperature storage and the capacity retention rate after capacity recovery according to the following formulas.
Internal resistance change rate = ((internal resistance value after full charge state high temperature storage-internal resistance value before full charge state high temperature storage)/internal resistance value before full charge state high temperature storage) 100%
Capacity retention after high temperature storage= (discharge capacity after high temperature storage/initial capacity) ×100%
Capacity retention after capacity recovery= (highest capacity/initial capacity within 3 weeks after high-temperature storage discharge) ×100%
And a high-low temperature discharge test step: charging at 25 ℃ with a current of 0.33 ℃ and constant current and constant voltage until the limiting voltage reaches 4.4V, and ending the charging when the cut-off current is reduced to 0.02 ℃; the discharge is ended when the constant current discharge reaches the cut-off voltage of 3.0V at 25 ℃ with the current of 0.33C, and the initial capacity is taken as the initial capacity; after charging at 25 ℃ according to the above procedure, discharging to 3.0V at-20 ℃ and 55 ℃ respectively, and recording the discharge capacity, the capacity retention at-20 ℃ and 55 ℃ respectively was calculated from the following formula:
-20 ℃ discharge capacity retention = (-20 ℃ discharge capacity/initial capacity) ×100%
55 ℃ discharge capacity retention = (55 ℃ discharge capacity/initial capacity) ×100%
And (3) a cyclic test step: placing the battery cell into a Xinwei test cabinet, charging at 25 ℃ with 1C current and constant voltage until the limit voltage reaches 4.4V, and ending the charging when the cut-off current is reduced to 0.02C; discharging is finished when the constant current is discharged to the cut-off voltage of 3.0V by using the current of 1C, and the initial capacity is taken as the initial capacity; the charge and discharge were carried out at 25℃for 400 weeks according to the above procedure, and after the completion, the weekly discharge capacities were recorded, respectively, and the capacity retention was calculated from the following formula:
capacity retention= (weekly discharge capacity/initial capacity) ×100%
Table 4.1-19 test data for batteries under different conditions (wherein the electrolytes used for battery 1# -19 correspond to the electrolytes of application comparative examples 1-2 and application examples 1-17, respectively)
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As is clear from the above table, the use of 3, 6-bis (allyloxy) phthalonitrile prepared in example 1 as an additive for lithium ion electrolyte was applied to the battery, and the overall performance of the battery was best when the additives were 4.0wt% fluoroethylene carbonate and 0.5wt%3, 6-bis (allyloxy) phthalonitrile, respectively.
On the basis, the mass contents of the solvent, the additive and the lithium salt which form the electrolyte are further optimized, and the newly synthesized additive is applied to the lithium cobalt oxide battery by adopting the electrolyte proportion, so that the addition of the 2, 3-dicyanohydroquinone derivative can be found, and the high-low temperature performance and the cycle performance of the lithium ion battery can be greatly improved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary or exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A 2, 3-dicyanohydroquinone derivative having a structural formula represented by the general formula:
wherein R is 1 ，R 2 Is a straight chain, branched chain alkene or alkyne containing from 2 to 6 carbon atoms.
2. A 2, 3-dicyanohydroquinone derivative as claimed in claim 1, wherein: the structural formula comprises any one of the following structures:
3. a process for the synthesis of a 2, 3-dicyanohydroquinone derivative as claimed in claim 1 or 2, characterised by the steps of:
under the protection of nitrogen, 2, 3-dicyano hydroquinone and halogenated alkene or alkyne undergo nucleophilic substitution reaction to obtain 2, 3-dicyano hydroquinone derivatives, wherein the reaction is as follows:
wherein X is a halogen atom.
4. A method for synthesizing a 2, 3-dicyanohydroquinone derivative as claimed in claim 3, wherein: 2, 3-dicyanohydroquinone and R in the synthesis reaction 1 The molar ratio of X is as follows: 1:1 to 1.2;
2, 3-dicyanohydroquinone and R in the synthesis reaction 2 The molar ratio of X is as follows: 1:1 to 1.2.
5. A method for synthesizing a 2, 3-dicyanohydroquinone derivative as claimed in claim 3, wherein: the reaction temperature in the synthesis reaction is-10 ℃ to 100 ℃.
6. A method for synthesizing a 2, 3-dicyanohydroquinone derivative as claimed in claim 3, wherein: the synthetic reaction time is 2-24 h.
7. A method for synthesizing a 2, 3-dicyanohydroquinone derivative as claimed in claim 3, wherein: the reaction solvent in the synthesis reaction is N, N-dimethylformamide, acetone, acetonitrile or dimethyl sulfoxide in an aprotic polar solvent; the base used in the reaction is potassium carbonate, sodium carbonate or sodium bicarbonate in an inorganic base, or triethylamine, isopropylamine, diisopropylamine, or pyridine in an organic base.
8. A process for the synthesis of 2, 3-dicyanohydroquinone derivatives according to claim 3, characterized in that:
and (3) crystallizing and purifying the crude product obtained after the synthesis reaction to obtain the target product, namely the 2, 3-dicyanohydroquinone derivative.
9. A lithium ion battery electrolyte, characterized by comprising a lithium salt, an organic solvent and an additive, wherein the additive consists of the 2, 3-dicyanohydroquinone derivative and fluoroethylene carbonate according to claim 1 or 2; the mass percentage of the 2, 3-dicyano hydroquinone derivative is 0-1.5wt%, and the mass percentage of the fluoroethylene carbonate is 0-4.0wt%.
10. The lithium ion battery electrolyte according to claim 9, wherein the lithium salt is 12.50% by mass and the organic solvent is 82% -87.5% by mass.
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