CN117650280A - Lithium ion battery electrolyte additive and synthesis method and application thereof - Google Patents
Lithium ion battery electrolyte additive and synthesis method and application thereof Download PDFInfo
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- CN117650280A CN117650280A CN202311752017.8A CN202311752017A CN117650280A CN 117650280 A CN117650280 A CN 117650280A CN 202311752017 A CN202311752017 A CN 202311752017A CN 117650280 A CN117650280 A CN 117650280A
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- hydroxymethyl
- lithium ion
- ion battery
- methyl acrylate
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 31
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000004756 silanes Chemical class 0.000 claims abstract description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- -1 lithium hexafluorophosphate Chemical group 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 208000028659 discharge Diseases 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- RFUCOAQWQVDBEU-UHFFFAOYSA-N methyl 2-(hydroxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)CO RFUCOAQWQVDBEU-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 125000005336 allyloxy group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000003442 weekly effect Effects 0.000 description 2
- XXOSFUYRYSLQEN-UHFFFAOYSA-N 3,3,3-tribromoprop-1-ene Chemical compound BrC(Br)(Br)C=C XXOSFUYRYSLQEN-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 group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [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
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 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
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- FPHBLZMNRWNJEJ-UHFFFAOYSA-N methyl 2-(prop-2-enoxymethyl)prop-2-enoate Chemical compound COC(=O)C(=C)COCC=C FPHBLZMNRWNJEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
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- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery electrolyte additive, a synthesis method and application thereof. The additive is a 2- (hydroxymethyl) methyl acrylate derivative. The additive is prepared by adopting a synthesis reaction of nucleophilic substitution of raw material 2- (hydroxymethyl) methyl acrylate and halogenated silane or halogenated olefin. The synthesis method is a one-step synthesis method, the synthesis process is simpler, and the yield and purity are high. The invention also discloses application of the additive in lithium ion battery electrolyte. The invention applies the additive to the lithium ion electrolyte, can improve the problem of overlarge internal resistance of the battery, reduce internal resistance change before and after high-temperature storage, and improve the cycle life and high-temperature storage performance of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to lithium ion battery electrolyte, an additive and a synthesis method thereof.
Background
The lithium ion battery has the advantages of high specific energy, high energy storage efficiency, long cycle life and the like, so that the lithium ion battery gradually occupies the main market share of energy carriers of electric automobiles, energy storage systems and mobile electronic equipment in recent years, and along with the progress of society and the improvement of the material level of people, the requirements of people on the lithium ion battery are higher and higher.
When the lithium ion battery is charged, a layer of composite electrolyte membrane is formed on the surface of the negative electrode, so that the direct contact reaction of the electrolyte and the negative electrode is effectively avoided. The conventional film forming additive participates in reaction film forming before the decomposition of the carbonic acid base solvent, so that the consumption of electrolyte and the capacity loss in the subsequent circulating process are reduced, but the internal resistance of the battery is overlarge, a large amount of irreversible joule heat is generated, various performances of the lithium ion battery are influenced, and the circulating performance of the lithium ion battery is reduced.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides an electrolyte additive for lithium ion batteries, which is prepared by adding a 2- (hydroxymethyl) methyl acrylate derivative as an additive to an electrolyte, thereby improving the problem of excessive internal resistance of the battery, reducing internal resistance change before and after high-temperature storage, and improving cycle life and high-temperature storage performance of the battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows.
The invention firstly provides an electrolyte additive of a lithium ion battery, wherein the additive is one or more of 2- (hydroxymethyl) methyl acrylate derivatives. More specifically, the general structural formula of the 2- (hydroxymethyl) methyl acrylate derivative is as follows:
wherein R is 1， R 2， R 3 Linear or branched alkanes of 1 to 3 carbon atoms; r is R 4 Is a linear or branched olefin having 2 to 6 carbon atoms, or a linear or branched olefin having 2 to 6 carbon atoms containing an element F.
The invention also provides a synthesis method of the battery electrolyte additive 2- (hydroxymethyl) methyl acrylate derivative, which comprises the following steps:
under the protection of nitrogen, taking raw material 2- (hydroxymethyl) methyl acrylate, a reaction solvent and alkali, and dropwise adding halogenated silane or halogenated olefin to carry out nucleophilic substitution synthesis reaction to obtain the 2- (hydroxymethyl) methyl acrylate derivative.
Wherein the synthesis reaction of the 2- (hydroxymethyl) methyl acrylate and the halogenated silane is as follows:
wherein the synthesis reaction of the methyl 2- (hydroxymethyl) acrylate and the halogenated olefin is as follows:
further, the molar ratio of the methyl 2- (hydroxymethyl) acrylate to the halosilane or the haloolefin in the synthesis reaction is as follows: 1:1 to 2;
further, the reaction temperature of the synthesis reaction is-10 ℃ to 40 ℃ and the reaction time is 2 to 6 hours.
Further, the reaction solvent of the synthesis reaction is a nonpolar solvent such as dichloromethane, chloroform, toluene and the like; the base used in the reaction is an inorganic base such as potassium carbonate, sodium hydrogencarbonate, or an organic base such as triethylamine, isopropylamine, diisopropylamine, or pyridine.
Further, the crude product obtained after the synthesis reaction is subjected to column purification or rectification to obtain the target product, namely the 2- (hydroxymethyl) methyl acrylate derivative.
The invention also provides lithium ion battery electrolyte, which comprises the components of lithium salt, organic solvent and additive. Wherein the additive is one or more of 2- (hydroxymethyl) methyl acrylate derivatives; the mass of the 2- (hydroxymethyl) methyl acrylate derivative accounts for 0-5.0% of the total mass of the electrolyte, and more preferably 0.5-2.5%.
The lithium salt is selected from lithium hexafluorophosphate, and the mass percentage of the lithium salt in the electrolyte is 12.50%.
The organic solvent is a mixed solvent of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate, and the mass ratio of the three is 1:1:1.
the invention provides a lithium ion battery electrolyte additive 2- (hydroxymethyl) methyl acrylate derivative and synthesis and application thereof in lithium ion battery electrolyte. The additive is synthesized by adopting a one-step synthesis method, the synthesis process is simpler, and the yield and purity are high. The 2- (hydroxymethyl) methyl acrylate derivative is used as an additive to be applied to lithium ion electrolyte, so that the problem of overlarge internal resistance of the battery can be solved, the internal resistance change before and after high-temperature storage is reduced, and the cycle life and high-temperature storage performance of the battery are improved.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of methyl 2- (((trimethylsilyl) oxy) methacrylate) of example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of methyl 2- ((allyloxy) methyl) acrylate in example 5.
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 additive 2- (hydroxymethyl) methyl acrylate derivative in the invention is as follows:
wherein R is 1， R 2， R 3 Linear or branched alkanes of 1 to 3 carbon atoms; r is R 4 Is a linear or branched olefin having 2 to 6 carbon atoms, or a linear or branched olefin having 2 to 6 carbon atoms containing an element F. Examples the following specific structures are illustrated:
example 1
The structural formula of the additive 2- (((trimethylsilyl) oxy) methyl methacrylate) is as follows:
the synthesis steps of the additive are as follows:
13.22g (114 mmol 1.0 eq) of methyl 2- (hydroxymethyl) acrylate, 34.56g (342 mmol) of triethylamine and 130ml of methylene chloride were put into a 250ml three-necked flask, nitrogen was replaced three times, nitrogen protection was performed, and the temperature was lowered to-10℃by using an ice salt bath. 13.61g (125 mmol 1.1 eq) of trimethylchlorosilane is added dropwise, the internal temperature is controlled to be not higher than minus 10 ℃, the dropwise addition is completed, the reaction is carried out for 1h at a constant temperature, the reaction is carried out for 2h at room temperature slowly, and then the basic reaction is sampled.
Post-treatment: washing with 100ml saturated aqueous solution of ammonium chloride for 2 times, washing with 100ml pure water for 1 time, drying the organic phase with anhydrous sodium sulfate, filtering, and concentrating under reduced pressureThe crude product 19.32g yellow liquid is purified by a column to obtain 17.60g transparent clear liquid with the yield of 82.01 percent. The nuclear magnetism was confirmed to be the target product 2- (((trimethylsilyl) oxy) methyl methacrylate as shown in fig. 1. 2- (((trimethylsilyl) oxy) methyl) acrylate 1 H-NMR data (CDCl) 3 Internal standard: tetramethylsilane): d (ppm) 0.16 (S, 9H, -CH 3 )，3.78(S,3H，-CH 3 )，4.36-4.37(t,2H,-CH 2 )，5.91-5.92(dd,1H,＝CH)，6.28-6.29(dd,1H,＝CH)。
Examples 2 to 4
As with the reaction procedure of example 1, the specific synthetic 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 2-4
Example 5
The structure of additive 2- ((allyloxy) methyl) acrylate is as follows:
the synthesis steps are as follows:
15.30g (132 mmol, 1.0 eq) of methyl 2- (hydroxymethyl) acrylate; 39.97g (399mmol 3.0 eq) triethylamine; 150ml of methylene dichloride is put into a 250ml three-neck flask, nitrogen is replaced for three times, nitrogen protection is carried out, and the temperature is reduced to-10 ℃ by using an ice salt bath. 19.16g (158 mmol 1.2 eq) of tribromopropene are added dropwise, the internal temperature is controlled to be not higher than-10 ℃, the dropwise addition is completed, the reaction is slowly carried out until the reflux reaction is carried out for 4 hours, and then the basic reaction is sampled.
Post-treatment: 110ml of saturated aqueous solution of ammonium chloride is washed for 2 times, 110ml of pure water is washed for 1 time, the organic phase is dried by anhydrous sodium sulfate, filtered and concentrated under reduced pressure to obtain 18.83g of crude product, and 15.80g of light yellow transparent clear liquid is obtained after column purification, and the yield is 76.70%. Nuclear magnetism is confirmed to be a target product 2- ((allyloxy) methyl) Methyl acrylate, as shown in figure 2. 2- ((allyloxy) methyl) acrylic acid methyl ester 1 H-NMR data (CDCl 3, internal standard: tetramethylsilane) delta 3.77 (S, 3H), 4.04-4.07 (m, 2H), 4.20-4.21 (m, 2H), 5.19-5.23 (m, 1H), 5.28-5.34 (m, 1H), 5.89-5.97 (m, 2H), 6.31-6.32 (m, 1H).
Examples 6 to 8
As with the reaction procedure of example 5, 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 6-8
Application examples 1 to 24
The electrolyte was prepared using the additive 2- (hydroxymethyl) acrylic acid methyl ester 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 85-87.5wt% of organic solvent (ethylene carbonate/methyl ethyl carbonate/diethyl carbonate in a mass ratio of about 1:1:1), adding 12.50wt% of lithium hexafluorophosphate, stirring for dissolution, and finally adding 0-2.5wt% of one of the 2- (hydroxymethyl) methyl acrylate derivatives prepared in examples 1-8 as electrolyte additives, and stirring uniformly to obtain different lithium ion battery electrolytes.
Comparative example 1 was used
The electrolyte prepared in comparative example was used without adding the methyl 2- (hydroxymethyl) acrylate 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 contents of application examples 1-24 and application comparative example 1
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=96.0: 2.0:2.0; the formula of the negative electrode comprises the following steps: artificial graphite S360: SP: CMC2200: LA136 d=96.5: 1.0:0.5:2.0; the separator is a PE separator with the thickness of 16 mu m, the negative current collector is a copper foil with the thickness of 12 mu m, and the positive current collector is an aluminum foil with the thickness of 16 mu m.
Test part
The electrolytes prepared in application comparative example 1 and application examples 1 to 24 were injected into the above-prepared batteries, corresponding to batteries 1 to 25, respectively, and the cycle performance and high-temperature storage performance of the batteries were tested, 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 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 high-temperature storage in full-charge state-internal resistance value before high-temperature storage in full-charge state)/internal resistance value before high-temperature storage in full-charge state) value of 100%
Capacity retention after high temperature storage= (discharge capacity after high temperature storage/initial capacity) ×100%
Capacity recovery = (highest capacity/initial capacity in 3 weeks after high temperature storage discharge) 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 500 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 high temperature storage and cycling data for batteries 1-25
Through testing the normal temperature cycle performance and the high temperature storage performance of the lithium battery prepared by the embodiment, the invention discovers that the application of the prepared 2- (hydroxymethyl) methyl acrylate derivative as the lithium ion electrolyte additive to the lithium battery can improve the cycle capacity retention rate of the lithium battery, reduce the internal resistance of the battery after circulation, reduce the internal resistance change rate in high temperature storage and improve the discharge capacity and the capacity recovery rate after high temperature storage, so that the application of the prepared 2- (hydroxymethyl) methyl acrylate derivative to the lithium battery can improve the high temperature storage performance and the cycle performance of the lithium battery.
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. An electrolyte additive for a lithium ion battery is characterized in that: the additive is one or more of 2- (hydroxymethyl) methyl acrylate derivatives.
2. The lithium ion battery electrolyte additive according to claim 1, wherein: the general structural formula of the 2- (hydroxymethyl) methyl acrylate derivative is as follows:
wherein R is 1， R 2， R 3 Linear or branched alkanes of 1 to 3 carbon atoms;
R 4 is a linear or branched olefin having 2 to 6 carbon atoms, or a linear or branched olefin having 2 to 6 carbon atoms containing an element F.
3. A method for synthesizing a lithium ion battery electrolyte additive according to claim 1 or 2, comprising the steps of:
under the protection of nitrogen, taking raw material 2- (hydroxymethyl) methyl acrylate, a reaction solvent and alkali, and dropwise adding halogenated silane or halogenated olefin to carry out nucleophilic substitution synthesis reaction to obtain the 2- (hydroxymethyl) methyl acrylate derivative;
wherein, the synthesis reaction of the 2- (hydroxymethyl) methyl acrylate and the halogenated silane is as follows:
wherein, the synthesis reaction of the 2- (hydroxymethyl) methyl acrylate and the halogenated olefin is as follows:
4. a method for synthesizing a lithium ion battery electrolyte additive according to claim 3, wherein: the molar ratio of the 2- (hydroxymethyl) methyl acrylate to the halosilane or the haloolefin in the synthesis reaction is as follows: 1:1 to 2.
5. A method for synthesizing a lithium ion battery electrolyte additive according to claim 3, wherein: the reaction temperature of the synthesis reaction is-10 ℃ to 40 ℃ and the reaction time is 2 to 6 hours.
6. A method for synthesizing a lithium ion battery electrolyte additive according to claim 3, wherein: the reaction solvent is a nonpolar solvent selected from dichloromethane, chloroform or toluene;
the alkali is inorganic alkali or organic alkali, wherein the inorganic alkali is selected from potassium carbonate, sodium carbonate or sodium bicarbonate, and the organic alkali is selected from triethylamine, isopropylamine, diisopropylamine or pyridine.
7. A method for synthesizing a lithium ion battery electrolyte additive according to claim 3, wherein: and (3) obtaining a crude product after the synthesis reaction, and purifying or rectifying the crude product by a column to obtain a target product, namely the 2- (hydroxymethyl) methyl acrylate derivative.
8. The lithium ion battery electrolyte comprises the following components of lithium salt, an organic solvent and an additive; the method is characterized in that: wherein the additive is one or more of the 2- (hydroxymethyl) methyl acrylate derivatives of claim 1 or 2; the mass of the 2- (hydroxymethyl) methyl acrylate derivative accounts for 0-5.0% of the total mass of the electrolyte.
9. The lithium ion battery electrolyte according to claim 8, wherein: the mass of the 2- (hydroxymethyl) methyl acrylate derivative accounts for 0.5-2.5% of the total mass of the electrolyte.
10. The lithium ion battery electrolyte according to claim 8, wherein: the lithium salt is lithium hexafluorophosphate, and the mass percentage of the lithium salt in the electrolyte is 12.50%; the organic solvent is a mixed solvent of ethylene carbonate, ethylmethyl carbonate and diethyl carbonate, and the mass ratio of the three is 1:1:1.
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