CN112375061A - Electrolyte film forming additive, synthesis method and application thereof - Google Patents
Electrolyte film forming additive, synthesis method and application thereof Download PDFInfo
- Publication number
- CN112375061A CN112375061A CN202011250454.6A CN202011250454A CN112375061A CN 112375061 A CN112375061 A CN 112375061A CN 202011250454 A CN202011250454 A CN 202011250454A CN 112375061 A CN112375061 A CN 112375061A
- Authority
- CN
- China
- Prior art keywords
- film
- forming additive
- electrolyte
- additive
- carbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000654 additive Substances 0.000 title claims abstract description 59
- 230000000996 additive effect Effects 0.000 title claims abstract description 57
- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- 238000001308 synthesis method Methods 0.000 title claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical group OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 claims abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 239000012043 crude product Substances 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- -1 benzene compound Chemical class 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical group O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 4
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910006819 Li1+xNiO2 Inorganic materials 0.000 claims description 2
- 229910000552 LiCF3SO3 Inorganic materials 0.000 claims description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 claims description 2
- 229910013119 LiMxOy Inorganic materials 0.000 claims description 2
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 claims description 2
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 claims description 2
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to an electrolyte film-forming additive, a synthesis method and application thereof, wherein the additive is mainly a film-forming additive, benzene rings and glycerol carbonate groups of the additive can quickly act on the surface of a negative electrode, the interface of the electrolyte between the negative electrodes is improved, a stable and compact SEI film is quickly formed on the surface of the negative electrode, the decomposition of the electrolyte is inhibited, a solvent and other additives are limited to be embedded into the surface of the negative electrode, the surface of the negative electrode is prevented from being damaged, the cycle performance of a battery can be improved, and the cycle life is effectively prolonged.
Description
Technical Field
The invention relates to the field of liquid batteries, in particular to an electrolyte film-forming additive, a synthesis method and application thereof.
Background
The research of the lithium ion battery electrolyte and the functional additive has become a focus of the current lithium ion battery research, the performance of the organic solvent and the electrolyte directly influences the working performance of the lithium ion battery, the safety performance of the lithium ion battery is more and more emphasized, and the search for the additive for improving the safety performance of the lithium ion battery has become a primary task of the research, and at present, the main focus of the research of the lithium ion battery electrolyte functional additive is to improve the stability of an SEI film: the invention provides an electrolyte film-forming additive capable of quickly forming a film, which can quickly form a stable and compact SEI film in a formation stage, and can reduce the loss of the SEI film to lithium salts and prolong the cycle life of a battery in the battery cycle process of the stable and compact SEI film.
Disclosure of Invention
The invention aims to provide an electrolyte film-forming additive, a synthesis method and application thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: an electrolyte film-forming additive, characterized in that: the film forming additive is an ester additive, the main body of the film forming additive is a benzene ring, and H on the benzene ring is substituted to form a multi-position substituted benzene compound.
The structural formula is as follows:
wherein R includes R1、R2、R3…RNWherein the R substituent group is C1、C2、C3…CNThe R is a cyclic ester, the cyclic ester is trimethylene carbonate, propylene carbonate or 2, 3-cyclic glycerol carbonate, wherein the R is the alkylThe number of the substituted H is 2-4, and the raw materials for synthesizing the compound mostly containing the substituent benzene at the para position, the meta position or the 1, 2, 4 and 5 positions of a benzene ring comprise: a reaction host group, an R group ester, tetrahydrofuran, dichloromethane, acetone, and nitrogen, wherein the reaction host group is: terephthaloyl chloride, 1, 3, 5-trimesoyl chloride or 1, 2, 4, 5-pyromellitic chloride, wherein the R group is one or more of glycerol carbonate or linear esters.
The invention also provides a synthesis method of the electrolyte film-forming additive, which comprises the following steps:
s1, mixing R and a reaction main group according to the ratio of 3-4: 1, adding the mixture into anhydrous acetone according to the proportion, and reacting in an insulation box, wherein the environmental temperature of the insulation box is-10 ℃;
s2, flushing nitrogen for protection, stirring in a magnetic stirrer, controlling the rotating speed at 5000-;
s3, finally adding the crude product into dichloromethane for recrystallization to obtain the pure product.
The film forming additive can be applied to electrolyte and liquid lithium ion batteries.
The electrolyte consists of a solvent, lithium salt and a film forming additive.
The film forming additive is directly added into electrolyte to prepare the lithium ion battery, and the dosage of the film forming additive is as follows: 0.2-0.5 mol/L.
Wherein the lithium salt is: LiPF6、LiBF4、LiClO4、LiAsF6Or LiCF3SO3The dosage of the lithium salt is as follows: 1-1.5 mol/L.
Wherein the solvent is: ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), dimethyl carbonate (DMC), preferably with a solvent component EC: EMC of 1: 1.
The lithium ion battery anode material is as follows: LiMxOyXz(wherein M is a transition metal, X is a halogen element, and X, y, and z are natural numbers), LiCoO2、LiMnO2、LiFePO4，LiNi1-x-yCoxMnyO2、Li1+xNi1-yMnyO2、Li1+xNiO2、Li1+xCo1- yNiyO2(wherein x is more than or equal to 0.3 and more than or equal to-0.3, and y is more than or equal to 0.8 and more than or equal to 0.3), preferably: and a nickel cobalt lithium manganate compound 811.
The lithium ion battery negative electrode material is as follows: one or more of lithium metal, graphite and silicon carbon material, preferably lithium metal.
Wherein, the barrier film is a naked film made of PP or PE material.
The manufacturing method of the lithium ion battery comprises the following steps: respectively stirring positive and negative electrode materials into uniform slurry, coating the slurry on a foil, preparing a positive electrode plate and a negative electrode plate after cold pressing, slitting, die cutting and sheet making, preparing the positive electrode plate, an isolating membrane and the negative electrode plate into a bare cell through a winding or laminating process, and obtaining a finished battery after packaging, liquid injection, standing, formation, aging and capacity grading.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides synthesis and application of a film forming additive for lithium ion battery electrolyte, the additive is mainly a film forming additive, benzene rings and glycerol carbonate groups of the additive can quickly act on the surface of a negative electrode, the interface of the electrolyte between the negative electrodes is improved, a stable and compact SEI film is quickly formed on the surface of the negative electrode, the decomposition of the electrolyte is inhibited, a solvent and other additives are limited to be embedded into the surface of the negative electrode, the surface of the negative electrode is prevented from being damaged, the cycle performance of the battery can be improved, and the cycle life is effectively prolonged.
Drawings
FIG. 1: structural formula of film forming additive
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The lithium ion battery anode material is selected from the following materials: and a nickel cobalt lithium manganate compound 811.
Wherein, the lithium ion battery cathode is selected from: graphite.
Wherein, the lithium ion battery isolating membrane is selected from the following components: and (3) PE films.
The manufacturing method of the lithium ion battery comprises the following steps: respectively stirring positive and negative electrode materials into uniform slurry, coating the slurry on a foil, preparing a positive electrode plate and a negative electrode plate after cold pressing, slitting, die cutting and sheet making, preparing the positive electrode plate, an isolating membrane and the negative electrode plate into a bare cell through a winding or laminating process, and obtaining a finished battery after packaging, liquid injection, standing, formation, aging and capacity grading.
Wherein the electrolyte is selected from the following comparative examples and examples:
comparative example 1
The electrolyte of the comparative example is selected from the following basic electrolytes:
the electrolyte formula is as follows: EC and EMC are 1 to 1, and the film-forming additive is selected from common VC: 0.2mol/L, LiPF6,1.5mol/L
Example 1
Synthesis of a film forming additive: r is 2, 3-cyclic carbonate glyceride, and the 2, 3-cyclic carbonate glyceride and the terephthaloyl chloride are mixed according to the weight ratio of 3: 1, adding the mixture into anhydrous acetone, controlling the environmental temperature at-10 ℃, introducing nitrogen for protection, rotating at the rotation speed of 10000rmp, reacting for 18 hours to generate a crude product, and adding the crude product into dichloromethane for recrystallization to obtain a pure product A;
preparing the film forming additive A into electrolyte, wherein the electrolyte formula comprises the following components: the electrolyte solvent is: EC and EMC are 1 to 1, and the dosage of the film-forming additive A is as follows: 0.2mol/L, lithium salt is: LiPF6And the dosage is as follows: 1.5 mol/L.
Example 2
The synthesis method of the film forming additive comprises the following steps: r is 2, 3-cyclic carbonate glyceride, and the 2, 3-cyclic carbonate glyceride and 1, 3, 5-trimesoyl chloride are mixed according to the weight ratio of 3.5: 1, adding the mixture into anhydrous acetone, controlling the environmental temperature at 0 ℃, introducing nitrogen for protection, reacting for 12 hours at a rotation speed of 8000rmp to generate a crude product, and adding the crude product into dichloromethane for recrystallization to obtain a pure product B;
preparing the film forming additive B into an electrolyte: the electrolyte formula is as follows: the electrolyte solvent is: EC and EMC are 1 to 1, and the dosage of the film-forming additive B is as follows: 0.3mol/L, lithium salt is: LiPF6And the dosage is as follows: 1.3 mol/L.
Example 3
The synthesis method of the film forming additive comprises the following steps: r is 2, 3-cyclic carbonate glyceride, and the 2, 3-cyclic carbonate glyceride and 1, 2, 4, 5-pyromellitic dianhydride are mixed according to the ratio of 4: 1, adding the mixture into anhydrous acetone, controlling the environmental temperature at 10 ℃, introducing nitrogen for protection, rotating at the self-rotation speed of 5000rmp, reacting for 6 hours to generate a crude product, and adding the crude product into dichloromethane for recrystallization to obtain a pure product C;
preparing the film forming additive C into an electrolyte: the electrolyte formula is as follows: the electrolyte solvent is: EC and EMC are 1 to 1, and the dosage of the film-forming additive C is as follows: 0.4mol/L, lithium salt is: LiPF6And the dosage is as follows: 1.0 mol/L.
Example 4
The synthesis method of the film forming additive comprises the following steps: r is trimethylene carbonate, and the trimethylene carbonate and 1, 2, 4, 5-pyromellitic chloride are mixed according to the ratio of 4: 1, adding the mixture into anhydrous acetone, controlling the environmental temperature at 0 ℃, introducing nitrogen for protection, reacting for 12 hours at a rotation speed of 8000rmp to generate a crude product, and adding the crude product into dichloromethane for recrystallization to obtain a pure product D;
preparing the film forming additive D into an electrolyte: the electrolyte formula is as follows: the electrolyte solvent is: EC and EMC are 1 to 1, and the dosage of the film forming additive D is as follows: 0.5mol/L, lithium salt is: LiPF6And the dosage is as follows: 1.2 mol/L.
Example 5
The synthesis method of the film forming additive comprises the following steps: and R is propylene carbonate, and the propylene carbonate and 1, 2, 4, 5-pyromellitic dianhydride are mixed according to a ratio of 4: 1, adding the mixture into anhydrous acetone, controlling the environmental temperature at 0 ℃, introducing nitrogen for protection, reacting for 12 hours at a rotation speed of 8000rmp to generate a crude product, and adding the crude product into dichloromethane for recrystallization to obtain a pure product E;
preparing the film forming additive E into an electrolyte: the electrolyte formula is as follows: the electrolyte solvent is: EC and EMC are 1 to 1, and the dosage of the film-forming additive E is as follows: 0.5mol/L, lithium salt is: LiPF6And the dosage is as follows: 1.2 mol/L.
Injecting the electrolyte into a dry battery, standing, forming, aging and grading to obtain six-component batteries, and taking the batteries from each group to perform the following electrochemical performance test:
and (3) cycle testing:
in an environment of 25 ℃, the battery cell is charged to 4.2V at a constant current of 1C, is constant-voltage to 0.05C, is kept for 5min, is discharged to 2.75V at 1C, is kept for 5min, is charged to 4.2V at the constant current of 1C, is constant-voltage to 0.05C, is kept for 5min, is discharged to 2.75V at 1C, is kept for 5min, is circularly charged and discharged, and the percentage of the residual capacity of the battery cell after 500 cycles is recorded.
And (3) testing internal resistance after circulation:
and (3) carrying out internal resistance test on the circulating battery by using an internal resistance instrument before the test to record as R1, testing the internal resistance of the battery circulating for 100 weeks by using the internal resistance instrument to record as R2, and comparing the internal resistance increase in the circulating process.
The experimental results are as follows:
the test results show that the internal resistance of the system is obviously reduced and the cycle performance is obviously improved after the electrolyte of the film-forming additive is applied, so that the additive provided by the invention can form a layer of compact and uniform SEI film on the surface of graphite, effectively protect the point decomposition material, improve the cycle stability of the battery and obviously prolong the cycle life of the battery. The comparison shows that the 2, 3-cyclic glycerol carbonate is easier to form a stable SEI film than other two groups, the substance can effectively improve the interface between the electrolyte and the graphite, so that the internal resistance of the system is reduced from small to small, and a compact protective SEI film is formed, and the SEI film is not easy to decompose in the circulation process, so that the advantage that the internal resistance is increased to a small extent after circulation is displayed, and meanwhile, other organic solvents are limited to be embedded into the graphite cathode, so that the stability of the graphite cathode is protected, and the circulation life is prolonged.
The results of comparative experiments show that the synthetic route adopted in example 3 is as follows: r is 2, 3-cyclic carbonate glyceride, and the 2, 3-cyclic carbonate glyceride and 1, 2, 4, 5-pyromellitic dianhydride are mixed according to the ratio of 4: 1, adding the mixture into anhydrous acetone, controlling the environmental temperature at 10 ℃, introducing nitrogen for protection, rotating at the self-rotation speed of 5000rmp, reacting for 6 hours to generate a crude product, and adding the crude product into dichloromethane for recrystallization to obtain a pure product C; the product has the most obvious effect on the left and right surfaces of the negative electrode graphite and the best effect on improving the cycle performance of the battery.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. An electrolyte film-forming additive, characterized in that: the film forming additive is an ester additive, the main body of the film forming additive is a benzene ring, and H on the benzene ring is substituted to form a multi-position substituted benzene compound;
the structural formula is as follows:
wherein R includes R1、R2、R3…RNWherein the R substituent group is C1、C2、C3…CNThe ester substance of (1), wherein R is a cyclic ester, the cyclic ester is trimethylene carbonate, propylene carbonate or 2, 3-cyclic glycerol carbonate, the number of R-substituted H is 2-4, and the R-substituted H is at para position, meta position or 1, 2, 4, 5 position of a benzene ring, and the raw materials for synthesizing the compound mostly containing substituent benzene comprise: a reaction host group, an R group ester, tetrahydrofuran, dichloromethane, acetone, and nitrogen, wherein the reaction host group is: terephthaloyl chloride, 1, 3, 5-trimesoyl chloride or 1, 2, 4, 5-pyromellitic tetrachloride, wherein the radical R is glycerol carbonate or a linear ester.
2. The synthesis method of the electrolyte film-forming additive is characterized by comprising the following steps:
s1, mixing R and a reaction main group according to the ratio of 3-4: 1, adding the mixture into anhydrous acetone according to the proportion, and reacting in an insulation box, wherein the environment temperature of the insulation box is-10 ℃;
s2, flushing nitrogen for protection, stirring in a magnetic stirrer, controlling the rotating speed at 5000-;
s3, finally adding the crude product into dichloromethane for recrystallization to obtain the pure product.
3. The application of the electrolyte film-forming additive is characterized in that the film-forming additive can be applied to electrolyte and liquid lithium ion batteries.
4. Use of a film forming additive for an electrolyte according to claim 3, wherein the electrolyte is composed of a solvent, a lithium salt, and a film forming additive.
5. The use of the electrolyte film-forming additive according to claim 3, wherein the film-forming additive is added directly to the electrolyte to form a lithium ion battery, wherein the amount of the film-forming additive is as follows: 0.2-0.5 mol/L.
6. Use of the film forming additive for electrolytes according to claim 4, wherein said lithium salt is: LiPF6、LiBF4、LiClO4、LiAsF6Or LiCF3SO3The dosage of the lithium salt is as follows: 1-1.5 mol/L.
7. Use of an electrolyte film-forming additive according to claim 4, wherein the solvent is: ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), dimethyl carbonate (DMC).
8. The use of the electrolyte film-forming additive according to claim 3, wherein the positive electrode material in the lithium ion battery is: LiMxOyXz(wherein M is a transition metal, X is a halogen element, and X, y, and z are natural numbers), LiCoO2、LiMnO2、LiFePO4，LiNi1-x-yCoxMnyO2、Li1+xNi1-yMnyO2、Li1+xNiO2、Li1+xCo1-yNiyO2(wherein x is more than or equal to 0.3 and more than or equal to-0.3, and y is more than or equal to 0.8 and more than or equal to 0.3), wherein the lithium ion battery comprises the following negative electrode materials: one or more of lithium metal, graphite and silicon carbon materials, and the isolating film is a naked film made of PP or PE materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011250454.6A CN112375061A (en) | 2020-11-11 | 2020-11-11 | Electrolyte film forming additive, synthesis method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011250454.6A CN112375061A (en) | 2020-11-11 | 2020-11-11 | Electrolyte film forming additive, synthesis method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112375061A true CN112375061A (en) | 2021-02-19 |
Family
ID=74578566
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011250454.6A Pending CN112375061A (en) | 2020-11-11 | 2020-11-11 | Electrolyte film forming additive, synthesis method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112375061A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013093346A1 (en) * | 2011-12-19 | 2013-06-27 | Centre National De La Recherche Scientifique | Web of vegetable wool fibres of which the mechanical cohesion is ensured by a thermoplastic polymer binder |
| CN105006595A (en) * | 2015-08-18 | 2015-10-28 | 天津科技大学 | Electrolyte additive based on glycerol carbonate compounds and lithium ion battery |
| CN108832201A (en) * | 2018-06-06 | 2018-11-16 | 天津科技大学 | A kind of electrolysis additive, electrolyte and the lithium ion battery using it |
| CN109216762A (en) * | 2018-09-18 | 2019-01-15 | 哈尔滨工业大学无锡新材料研究院 | Carbonic acid glyceride (methyl) acrylate base polymer electrolyte of ultraviolet polymerization suitable for lithium secondary battery and preparation method thereof |
-
2020
- 2020-11-11 CN CN202011250454.6A patent/CN112375061A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013093346A1 (en) * | 2011-12-19 | 2013-06-27 | Centre National De La Recherche Scientifique | Web of vegetable wool fibres of which the mechanical cohesion is ensured by a thermoplastic polymer binder |
| CN105006595A (en) * | 2015-08-18 | 2015-10-28 | 天津科技大学 | Electrolyte additive based on glycerol carbonate compounds and lithium ion battery |
| CN108832201A (en) * | 2018-06-06 | 2018-11-16 | 天津科技大学 | A kind of electrolysis additive, electrolyte and the lithium ion battery using it |
| CN109216762A (en) * | 2018-09-18 | 2019-01-15 | 哈尔滨工业大学无锡新材料研究院 | Carbonic acid glyceride (methyl) acrylate base polymer electrolyte of ultraviolet polymerization suitable for lithium secondary battery and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 肖大刚: "碳酸甘油酯衍生物用于电解液添加剂的研究", 中国优秀硕士学位论文全文数据库工程科技Ⅱ辑, no. 4, 15 April 2018 (2018-04-15), pages 042 - 1146 * |
| 郭梦雅等: "新型锂离子电池电解液添加剂的合成与应用", 高等学校化学学报, vol. 38, no. 10, 10 October 2017 (2017-10-10), pages 1857 - 1863 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101881445B1 (en) | Non-aqueous electrolyte secondary battery | |
| EP2610958B1 (en) | Non-aqueous electrolyte and electrochemical device comprising the same | |
| CN101682080B (en) | Non-aqueous electrolyte and electrochemical device having the same | |
| CN102646847B (en) | Lithium rechargeable battery and its electrolyte | |
| CN109638353B (en) | Battery electrolyte additive, electrolyte containing additive and application of electrolyte | |
| WO2018099097A1 (en) | Electrolyte and secondary lithium battery | |
| CN103797635A (en) | Non-aqueous electrolyte secondary battery | |
| CN110336075B (en) | Electrolyte solution, electrochemical device and electronic device comprising same | |
| EP3352281B1 (en) | Non-aqueous electrolyte solution and non-aqueous electrolyte secondary battery | |
| CN109449511B (en) | Method for protecting lithium ion battery electrode | |
| CN110400969B (en) | Non-aqueous electrolyte and battery containing same | |
| WO2018120794A1 (en) | Electrolyte and secondary battery | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| CN107093765B (en) | Non-aqueous electrolyte and secondary battery | |
| CN102593513A (en) | Lithium ion secondary battery and electrolyte thereof | |
| CN113066975B (en) | Lithium ion battery | |
| US20040259002A1 (en) | Non-aqueous electrolyte and lithium secondary battery comprising same | |
| WO2018120787A1 (en) | Electrolyte and secondary battery | |
| WO2018120793A1 (en) | Electrolyte and secondary battery | |
| CN105811009B (en) | Electrolyte and lithium ion battery comprising same | |
| CN112216864A (en) | Lithium ion battery | |
| CN111200165B (en) | Electrolyte for lithium ion battery and lithium ion battery | |
| CN109309255A (en) | Electrolyte and electrochemical energy storage device | |
| CN112119530A (en) | Electrolyte solution, and electrochemical device and electronic device using same | |
| CN109390629B (en) | Electrolyte and battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |