CN111106387B - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN111106387B CN111106387B CN201911398706.7A CN201911398706A CN111106387B CN 111106387 B CN111106387 B CN 111106387B CN 201911398706 A CN201911398706 A CN 201911398706A CN 111106387 B CN111106387 B CN 111106387B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- -1 pyridyl compound Chemical class 0.000 claims abstract description 31
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical group 0.000 claims abstract description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 7
- 159000000002 lithium salts Chemical class 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 150000003464 sulfur compounds Chemical class 0.000 claims description 3
- CDUWJQGFRQTJHB-UHFFFAOYSA-N 1,3,2-dioxathiole 2,2-dioxide Chemical compound O=S1(=O)OC=CO1 CDUWJQGFRQTJHB-UHFFFAOYSA-N 0.000 claims description 2
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 150000004649 carbonic acid derivatives 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
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- LLEVMYXEJUDBTA-UHFFFAOYSA-N heptanedinitrile Chemical compound N#CCCCCCC#N LLEVMYXEJUDBTA-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- BTNXBLUGMAMSSH-UHFFFAOYSA-N octanedinitrile Chemical compound N#CCCCCCCC#N BTNXBLUGMAMSSH-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 125000004185 ester group Chemical group 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 230000001681 protective effect Effects 0.000 abstract 2
- 150000002500 ions Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007774 positive electrode material Substances 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011884 anode binding agent Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- 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
- H01M10/05—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
- H01M10/42—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte and a lithium ion battery. Lithium bis (oxalato) borate (LiBOB) and the cyano-containing pyridyl compound shown in the formula 1 are added into the electrolyte, wherein the cyano-containing pyridyl compound shown in the formula 1 can be chelated with an ester group contained in the electrolyte, a tough protective net is formed on the surface of the positive electrode, decomposition and gas production of the LiBOB at the positive electrode are inhibited, meanwhile, the LiBOB forms high impedance at the negative electrode, so that the LiBOB is more stable and is more favorable for forming an SEI film with high temperature performance, the two compounds form a stronger protective film on the surfaces of the positive electrode and the negative electrode together, a solvent contains low-viscosity n-propyl propionate, the addition of the n-propyl propionate is more favorable for ion conduction, the dynamic performance of the electrolyte is further improved, the impedance of the battery is reduced, the movement of lithium ions is smooth, and the high-low temperature performance and the safety performance of the battery are obviously improved.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to an electrolyte and a lithium ion battery.
Background
In recent years, with the rapid development of electronic products such as smart phones, tablet computers, smart wearing and the like, in consideration of the difference between the service life and the working environment of the electronic products, consumers have higher and higher requirements on the energy density and the service environment of a lithium ion battery, and meanwhile, along with the phenomenon of global warming, the lithium ion battery is required to have excellent high and low temperature performance.
At present, the energy density of the lithium ion battery is mainly improved by adopting a high-voltage lithium cobalt oxide anode material with 4.4V or more and a high-capacity high-compaction-density graphite cathode material. However, as the voltage of the lithium ion battery increases, the positive electrode active material becomes more oxidized, and a series of safety problems such as deterioration of high-temperature cycle performance of the high-voltage lithium ion battery and air blowing after the cycle occur. Under high temperature and high voltage, the electrolyte is easy to be oxidized and decomposed on the surface of the positive electrode to generate a large amount of gas, so that the battery bulges, the electrode interface is damaged, and the cycle performance of the battery is poor.
The electrolyte is used as an important component of the lithium ion battery, and has great influence on the electrical property of the battery. By optimizing the electrolyte additive, the electrolyte/electrode interface property is improved, the interface impedance is reduced, the oxidative decomposition gas production of the electrolyte can be effectively inhibited, and the dynamic performance of the lithium ion battery at low temperature can be improved. Therefore, it is very necessary to develop an electrolyte additive having excellent high and low temperature performance.
Disclosure of Invention
The invention aims to solve the problems that the high and low temperature performance of the existing lithium ion battery is difficult to be considered, the safety performance is poor and the like, and provides an electrolyte and the lithium ion battery.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an electrolyte comprising an organic solvent, a lithium salt and an additive, wherein the additive comprises lithium bis (oxalato) borate (LiBOB) and a cyano-containing pyridyl compound represented by formula 1; the using amount of the lithium bis (oxalato) borate (LiBOB) accounts for 0.1-2 wt% of the mass of the electrolyte; the using amount of the cyano-containing pyridyl compound shown in the formula 1 accounts for 0.1-5 wt% of the total mass of the electrolyte;
in the formula 1, R1、R2、R3And R4The same or different, each independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted C1-4Alkyl, or substituted or unsubstituted C1-4Alkoxy, said substituent being halogen or cyano.
Preferably, in formula 1, R1、R2、R3And R4The same or different, each independently selected from a hydrogen atom, a fluorine atom, or C1-4An alkoxy group.
According to the present invention, the cyano-containing pyridyl compound represented by formula 1 is selected from a compound represented by formula T1 or formula T2:
according to the present invention, the cyano group-containing pyridyl compound represented by said formula 1 is used in an amount of 0.1 to 5 wt%, preferably 0.1 to 2 wt%, based on the total mass of the electrolyte. For example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, or 5 wt%.
According to the invention, the lithium dioxalate borate (LiBOB) is used in an amount of 0.1 to 2 wt.%, preferably 0.1 to 1 wt.%, based on the mass of the electrolyte. For example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 1.8 wt%, or 2 wt%.
According to the present invention, the organic solvent comprises n-propyl propionate and at least one of the following organic solvents: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl acetate, n-butyl acetate, ethyl propionate.
According to the invention, the n-propyl propionate is used in an amount of 10 to 60 wt%, preferably 45 to 55 wt%, based on the total mass of the organic solvent. For example 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60 wt%.
According to the invention, the lithium salt is selected from lithium hexafluorophosphate.
According to the invention, the lithium salt is used in an amount of 10 to 18 wt% based on the total mass of the electrolyte. For example 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt% or 18 wt%.
According to the present invention, the electrolyte solution further includes one or more of other nitrile compounds, sulfur compounds, and carbonate compounds.
According to the invention, the other nitrile compound is preferably one or more of succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, glycerol trinitrile, ethoxypentafluorophosphazene, 1,3, 6-hexanetrinitrile.
According to the invention, the sulfur-containing compound is preferably one or more of 1, 3-propane sultone, 1, 3-propylene sultone, vinyl sulfate and vinylene sulfate.
According to the present invention, the carbonate compound is preferably one or more of ethylene carbonate, fluoroethylene carbonate, and ethylene carbonate.
According to the invention, the other nitrile compound, sulfur-containing compound and/or carbonate compound is used in an amount of 0 to 20 wt% based on the total mass of the electrolyte. For example, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 2.8 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, or 20 wt%.
The invention also provides a preparation method of the electrolyte, which comprises the following steps:
and mixing an organic solvent, a lithium salt and the additive to prepare the electrolyte.
The invention also provides a lithium ion battery which comprises the electrolyte.
According to the invention, the lithium ion battery also comprises a positive plate, a negative plate and a diaphragm, wherein the diaphragm is arranged between the positive plate and the negative plate. The diaphragm arranged between the positive plate and the negative plate can prevent the current short circuit caused by the contact of the two plates and can allow lithium ions to pass through.
According to the present invention, the anode includes an anode current collector and an anode active material layer disposed on one or both surfaces of the anode current collector.
Wherein, the negative current collector is selected from copper foil, such as electrolytic copper foil or rolled copper foil.
Wherein the anode active material layer includes an anode active material and an anode binder.
According to the present invention, the negative active material may be one or more of graphite, a silicon material, a silicon-carbon composite material, a silica material, an alloy material, and a lithium-containing metal composite oxide material.
According to the present invention, the positive electrode includes a positive electrode current collector and a positive electrode active material layer provided on one or both surfaces of the positive electrode current collector.
Wherein the positive electrode current collector is selected from aluminum foil.
Wherein the positive electrode active material layer includes a positive electrode active material and a positive electrode binder.
According to the present invention, the positive electrode active material is a lithium-containing compound. The lithium-containing compound includes one or more of a lithium transition metal composite oxide and a lithium transition metal phosphate compound.
According to the present invention, the positive electrode active material has a compacted density of 3.8 to 4.4mg/cm when applied3The negative electrode active material has a compacted density of 1.5 to 1.9mg/cm when applied3。
According to the invention, the separator is selected from porous films.
Wherein, the diaphragm is a porous film made of polymer.
The invention has the beneficial effects that:
the invention provides an electrolyte and a lithium ion battery. Lithium bis (oxalato) borate (LiBOB) and the cyano-containing pyridyl compound shown in formula 1 are added into the electrolyte, and the addition amount ranges of the two substances are selected (the research shows that the two substances have excellent synergistic effect when used in the ranges, and particularly, the description of the examples and the comparative examples can be seen), wherein the cyano-containing pyridyl compound shown in formula 1 can be chelated with an ester group contained in the electrolyte, a flexible protection net is formed on the surface of a positive electrode, the decomposition and gas production of the LiBOB on the positive electrode are inhibited, meanwhile, the LiBOB forms high impedance on a negative electrode, the solid electrolyte interface film (SEI film) with stable and high temperature performance is formed, the two compounds form stronger protection films on the surfaces of the positive electrode and the negative electrode together, and the solvent contains low-viscosity n-propyl propionate, which is added to facilitate ionic conduction, the dynamic performance of the electrolyte is further improved, the impedance of the battery is reduced, and the movement of lithium ions becomes smooth, so that the high-low temperature performance and the safety performance of the battery are obviously improved.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The cyano group-containing pyridyl compound represented by formula 1, which is referred to in the following examples and comparative examples, has the following structural formula:
comparative example 1
An organic solvent of ethylene carbonate/propylene carbonate/diethyl carbonate/n-propyl propionate was mixed at a mass ratio of 25:10:20:45, and 0.5 wt% of T1, 1 wt% of Vinylene Carbonate (VC), 3 wt% of 1, 3-Propane Sultone (PS) and 4 wt% of fluoroethylene carbonate (FEC) were added to the mixed solution as additives, based on the total mass of the electrolyte, and finally 1mol/L of lithium hexafluorophosphate was added to obtain an electrolyte of comparative example 1.
And injecting the electrolyte into the battery cell which is not injected with the electrolyte and comprises the positive plate, the negative plate and the diaphragm to prepare the lithium ion battery, thus obtaining the battery of the comparative example 1.
Example 1
An organic solvent of ethylene carbonate/propylene carbonate/diethyl carbonate/n-propyl propionate was mixed at a mass ratio of 25:10:20:45, and 0.5 wt% of T1, 0.5 wt% of LiBOB, 1 wt% of Vinylene Carbonate (VC), 3 wt% of 1, 3-Propane Sultone (PS) and 4 wt% of fluoroethylene carbonate (FEC) were added to the mixed solution as additives, based on the total mass of the electrolyte, and finally 1mol/L of lithium hexafluorophosphate was added to obtain an electrolyte of example 1.
The electrolyte was injected into an uninjected cell containing a positive electrode sheet, a negative electrode sheet, and a separator to prepare a lithium ion battery, and the battery of example 1 was obtained.
The composition and preparation method of other examples are the same as example 1 except for the differences shown in the following table 1; the compositions and preparation methods of the other comparative examples are the same as comparative example 1 except for the differences shown in the following table 1;
TABLE 1
Electrochemical performance tests were performed on the lithium ion batteries obtained in comparative examples 1 to 6 and examples 1 to 10 above
High temperature cycling experiment at 55 ℃: placing the batteries obtained in the examples 1-10 and the comparative examples 1-6 in an environment of (55 +/-2) DEG C, standing for 2-3 hours, when the battery body reaches (55 +/-2) DEG C, keeping the cut-off current of the battery at 0.05C according to 1C constant current charging, standing for 5 minutes after the battery is fully charged, then discharging to the cut-off voltage of 3.0V at 0.7C constant current, recording the highest discharge capacity of the previous 3 cycles as an initial capacity Q, and recording the last discharge capacity Q1 of the battery when the cycles reach the required times; and recording the initial thickness T of the battery cell, and recording the thickness T0 when the battery cell is selected and circulated to 300 weeks. And recording whether the battery produces gas after circulation. The results are reported in Table 2. The calculation formula used therein is as follows: capacity retention (%) ═ Q1/Q × 100%; thickness change rate (%) - (T0-T)/T × 100%;
low-temperature discharge experiment: the batteries obtained in examples 1-10 and comparative examples 1-6 were subjected to 10 charge-discharge cycles at a rate of 1.2C at room temperature, and then charged to a full charge state at a rate of 1.2C, and a 1.2C capacity Q was recorded0. Will be full ofThe battery in the electric state is placed at-20 ℃ for 4 hours, then discharged to 3V at 0.25C rate, and the discharge capacity Q is recorded3The low-temperature discharge capacity retention rate was calculated and reported in table 2. The low-temperature discharge capacity retention rate is calculated by the following formula: capacity retention (%) ═ Q3/Q0×100%。
TABLE 2 comparison of the results of the experiments of examples 1 to 10 and comparative examples 1 to 6
As can be seen from the results of table 2: the batteries of examples 1-10 had better high temperature cycle performance and low temperature discharge performance. It is understood from comparison of comparative examples 1 to 3 with examples 1 and 7 that the addition of a cyano group-containing pyridyl compound in combination with LiBOB significantly improves the after-cycle gassing phenomenon and improves the low-temperature discharge properties. It can be seen from comparison of comparative examples 4 and 5 with example 1 that the excessive addition of the cyano-containing pyridyl compound or LiBOB reduces the high and low temperature performance of the cell, because when the excessive addition of the additive is used, an ultra-thick SEI film is formed, which increases the cell impedance and greatly affects the cell dynamic performance. Compared with the embodiment 1 and the embodiment 7, the comparison example 6 shows that the low-temperature discharge performance can be greatly improved by adding the n-propyl propionate into the solvent, because the n-propyl propionate has lower viscosity, the electrolyte wettability is better, the dynamic performance of the electrolyte can be greatly improved, and the low-temperature performance of the battery cell can be improved.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. An electrolyte comprising an organic solvent, a lithium salt and an additive, wherein the additive comprises lithium bis (oxalato) borate (LiBOB) and a cyano group-containing pyridyl compound represented by formula 1; the using amount of the lithium bis (oxalato) borate (LiBOB) accounts for 0.1-2 wt% of the mass of the electrolyte; the using amount of the cyano-containing pyridyl compound shown in the formula 1 accounts for 0.1-5 wt% of the total mass of the electrolyte;
in the formula 1, R1、R2、R3And R4The same or different, each independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted C1-4Alkyl, or substituted or unsubstituted C1-4Alkoxy, said substituent being halogen;
the organic solvent comprises n-propyl propionate and at least one of the following organic solvents: ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, propyl acetate, n-butyl acetate, ethyl propionate.
2. The electrolyte as claimed in claim 1, wherein R in formula 11、R2、R3And R4The same or different, each independently selected from a hydrogen atom, a fluorine atom, or C1-4An alkoxy group.
4. the electrolyte solution according to claim 1, wherein the cyano group-containing pyridyl compound represented by formula 1 is used in an amount of 0.1 to 2 wt% based on the total mass of the electrolyte solution.
5. The electrolyte of claim 1, wherein the lithium bis (oxalato) borate (LiBOB) is used in an amount of 0.1 to 1 wt% based on the mass of the electrolyte.
6. The electrolyte of any of claims 1-5, wherein the n-propyl propionate is used in an amount of 10-60 wt% based on the total mass of the organic solvent.
7. The electrolyte of claim 6, wherein the n-propyl propionate is used in an amount of 45-55 wt% based on the total mass of the organic solvent.
8. The electrolyte of any of claims 1-5, wherein the lithium salt is selected from lithium hexafluorophosphate; the usage amount of the lithium salt accounts for 10-18 wt% of the total mass of the electrolyte.
9. The electrolyte of any one of claims 1-5, wherein the electrolyte further comprises one or more of other nitrile compounds, sulfur compounds, and carbonate compounds.
10. The electrolyte of claim 9, wherein the other nitrile compounds are selected from one or more of succinonitrile, glutaronitrile, adiponitrile, pimelonitrile, suberonitrile, glycerol trinitrile, ethoxypentafluorophosphazene, 1,3, 6-hexanetrinitrile.
11. The electrolyte of claim 9, wherein the sulfur-containing compound is selected from one or more of 1, 3-propane sultone, 1, 3-propene sultone, vinyl sulfate, and vinylene sulfate.
12. The electrolyte of claim 9, wherein the carbonate compound is selected from one or more of ethylene carbonate, fluoroethylene carbonate, and ethylene carbonate.
13. The electrolytic solution according to claim 9, wherein the other nitrile compound, sulfur compound and/or carbonate compound is used in an amount of 0 to 20 wt% based on the total mass of the electrolytic solution.
14. A lithium ion battery comprising the electrolyte of any of claims 1-13.
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