CN114530632A - Lithium ion battery electrolyte and lithium ion battery - Google Patents
Lithium ion battery electrolyte and lithium ion battery Download PDFInfo
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- CN114530632A CN114530632A CN202111605210.XA CN202111605210A CN114530632A CN 114530632 A CN114530632 A CN 114530632A CN 202111605210 A CN202111605210 A CN 202111605210A CN 114530632 A CN114530632 A CN 114530632A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 127
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 117
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 113
- -1 carboxylic ester compound Chemical class 0.000 claims abstract description 49
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 41
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 12
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 11
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 229940017219 methyl propionate Drugs 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 6
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 5
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 4
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- MOSDDXNHDFMSDW-UHFFFAOYSA-N methanesulfonic acid;prop-2-yn-1-ol Chemical compound OCC#C.CS(O)(=O)=O MOSDDXNHDFMSDW-UHFFFAOYSA-N 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- 150000001733 carboxylic acid esters Chemical class 0.000 abstract description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 10
- 239000010439 graphite Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 5
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 5
- 238000009830 intercalation Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 4
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000007784 solid electrolyte Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007614 solvation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Secondary Cells (AREA)
Abstract
The application discloses lithium ion battery electrolyte and a lithium ion battery. The electrolyte of the lithium ion battery comprises an organic solvent, a film forming agent and a lithium salt, wherein the organic solvent comprises a carboxylic ester compound; the film forming agent comprises a cyclic carbonate compound or/and a sulfonate compound; the molar concentration of the lithium salt is 2-4 mol/L. The lithium ion battery electrolyte containing the carboxylic ester organic solvent, the cyclic carbonate compound or/and the sulfonate film-forming agent and the high-concentration lithium salt has high ionic conductivity and a stable electrode interface structure, is simple in preparation process, has low requirements on equipment, and plays an important role in prolonging the cycle life and improving the capacity retention rate of the lithium ion battery in a low-temperature environment.
Description
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, large specific capacity, no memory effect and the like, and is widely applied to multiple fields of military equipment, electronic equipment, electric tools and the like. In recent years, lithium ion batteries have also been regarded as the most promising energy storage and conversion devices in electric vehicles. However, with the expansion of the application field of lithium ion batteries and the increasing demand for battery performance, researchers find that the low temperature environment can greatly limit the application performance of lithium ions.
The main reasons that the low temperature affects the performance of the lithium ion battery include: (1) the viscosity of the electrolyte is increased, and even part of the electrolyte is solidified, so that the ionic conductivity is reduced; (2) resistance of a solid electrolyte interface film (SEI) and resistance of charge transfer increase; (3) the solid phase diffusion ability of lithium ions is weakened. Besides the weakening of the solid-phase diffusion capacity of the lithium ions, the other two main reasons are closely related to the electrolyte, so that the development of the novel electrolyte has important significance for realizing the long cycle life and stable capacity retention rate of the lithium ion battery at low temperature.
Disclosure of Invention
The application provides a lithium ion battery electrolyte and a lithium ion battery, and aims to solve the problems of short cycle life and low capacity retention rate of the lithium ion battery in a low-temperature environment.
One aspect of the present application provides an electrolyte for a lithium ion battery, comprising an organic solvent, a film-forming agent, and a lithium salt, wherein,
the organic solvent comprises carboxylic ester compounds; the film forming agent comprises cyclic carbonate compounds or/and sulfonate compounds; the molar concentration of the lithium salt is 2-4 mol/L.
In an alternative embodiment of an aspect of the present application, the carboxylic acid ester-based compound includes one or more of methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, and methyl butyrate.
In an optional embodiment of an aspect of the present disclosure, the volume ratio of the organic solvent is 70 to 90% based on the total volume of the electrolyte.
In an alternative embodiment of an aspect of the present application, the cyclic carbonate-based compound includes one or more of fluoroethylene carbonate, ethylene carbonate, and vinylene carbonate.
In an alternative embodiment of one aspect of the present application, the sulfonate compound includes at least one of methanesulfonic acid-2-propyn-1-ol and 1, 3-propane sultone.
In an optional embodiment of an aspect of the present application, the film forming agent is 10 to 30% by volume based on the total volume of the electrolyte.
In an alternative embodiment of one aspect of the present application, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethanesulfonylimide, and lithium bistrifluoromethanesulfonylimide.
In an optional embodiment of an aspect of the present application, the lithium salt has a molar concentration of 2 to 3 mol/L.
Another aspect of the present application provides a lithium ion battery, including the above lithium ion battery electrolyte.
Compared with the prior art, the application has at least the following beneficial effects:
(1) the electrolyte of the lithium ion battery provided by the application has good ionic conductivity at low temperature.
On one hand, the lithium ion battery electrolyte takes the carboxylic ester compound as the organic solvent, so that the melting point and viscosity of an electrolyte system can be obviously reduced, and the ionic conductivity of the electrolyte system at low temperature is improved. On the other hand, lithium salts may promote Li+Solvation, increasing the carrier concentration in the electrolyte, and further improving the conductivity of the electrolyte.
(2) The electrolyte of the lithium ion battery is beneficial to maintaining the stability of the interface structure of the electrolyte of the electrode.
The cyclic carbonate or/and sulfonate film-forming agent and the high-concentration lithium salt can be reduced and decomposed together, wherein insoluble reduction products can be gradually deposited on the surface of an electrode material, so that a firm and thin solid electrolyte interface film is formed on the surface of an electrode, the stable ground electrode structure in the circulating process is ensured, the transmission distance of lithium ions in the interface film is shortened, and a good foundation is laid for further prolonging the circulating life of the battery.
(3) The preparation method of the lithium ion battery electrolyte provided by the application is simple, has low requirements on equipment, can be well compatible with the existing process, and has great large-scale application potential.
(4) The lithium ion battery provided by the application has good cycle life and capacity retention rate in a low-temperature environment.
According to the embodiment of the application, the lithium ion battery formed by the lithium ion battery electrolyte realizes stable circulation for over 240 circles under the charge-discharge current of 0.2C in the working environment of-20 ℃, the discharge capacity retention rate is still nearly 100%, and the average coulomb exceeds 99.91%. The lithium ion battery electrolyte is an electrolyte with research value and practical application potential.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for a person skilled in the art to obtain other drawings based on the drawings without any creative effort.
Fig. 1 is a diagram of electrochemical performance of a button lithium ion battery provided in embodiment 1 of the present application;
fig. 2 is an electrochemical performance diagram of a soft package lithium ion battery provided in embodiment 1 of the present application.
Detailed Description
In order to make the application purpose, technical solution and beneficial technical effects of the present application clearer, the present application is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present application and are not intended to limit the present application.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "a plurality" of "one or more" means two or more.
The above summary of the present application is not intended to describe each disclosed embodiment or every implementation of the present application. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In each instance, the list is merely a representative group and should not be construed as exhaustive.
At present, the viscosity of the electrolyte is increased and the ionic conductivity is reduced at low temperature; the SEI film has a large resistance to charge transfer; due to the reasons, the existing lithium ion battery electrolyte has low operation efficiency at low temperature, seriously influences the electrochemical performance of the battery, and is difficult to meet the use requirement of the prior art on the lithium ion battery.
Based on this, the inventors have conducted extensive studies with the aim of providing an electrolyte for a lithium ion battery having a small viscosity, a high ionic conductivity, and a low SEI film and a low charge transfer resistance in a low temperature environment, thereby imparting a good cycle life and a good capacity retention rate to a lithium ion battery comprising the electrolyte in a low temperature environment.
Lithium ion battery electrolyte
Embodiments of the first aspect of the present application provide a lithium ion battery electrolyte, including an organic solvent, a film forming agent, and a lithium salt, where the organic solvent includes a carboxylic ester compound; the film forming agent comprises cyclic carbonate compounds or/and sulfonate compounds; the molar concentration of the lithium salt is 2-4 mol/L.
According to the lithium ion battery electrolyte disclosed by the embodiment of the application, through selection of the organic solvent and the film forming agent and regulation and control of the lithium salt concentration, all components in the electrolyte act together, so that the lithium ion battery electrolyte has high conductivity and low impedance performance.
According to the embodiment of the application, compared with the electrolyte containing a vinyl carbonate group, propylene carbonate and the like, the carboxylic ester compound is used as the organic solvent, so that the melting point and the viscosity of the electrolyte system can be obviously reduced, the electrolyte system is ensured to have higher ionic conductivity at low temperature, and a good foundation is laid for efficient and stable operation of a lithium ion battery.
However, the carboxylate compounds in the examples of the present application have poor film-forming properties, and may cause co-intercalation of a solvent into the negative electrode material, resulting in peeling of the negative electrode material. Therefore, in the embodiments of the present application, the formation of the negative electrode/electrolyte interface SEI film is promoted by introducing a cyclic carbonate or/and sulfonate compound high-reactivity film-forming agent. During the charging process of the lithium ion battery, the film forming agent is reduced and decomposed to generate the poly (ethylene carbonate), LiF and Li2CO3And the products are attached to the surface of the negative electrode material to form an SEI film with a small thickness. The film has lower impedance, can prevent the co-intercalation of solvent molecules, weakens the damage to a negative electrode material caused by the co-intercalation of the solvent, and simultaneously has less loss to active lithium, thereby ensuring the good operation of the lithium ion battery at low temperature.
Further, in some nonaqueous electrolytic solutions, when the concentration of the lithium salt exceeds a certain threshold, the physicochemical properties of the bulk phase and the interface may be drastically changed, resulting in a change in properties other than a dilute solution. Compared with the conventional lithium salt electrolyte with high concentration, the lithium salt electrolyte with high concentration can form a layer of compact and tough solid electrolyte film on the surface of the negative electrode, and can reduce the side reaction between the electrode material and the electrolyte, thereby improving the safety performance of the battery. At the same time, Li in the high-concentration lithium salt electrolyte+The solvation number of (a) is decreased to cause solvation of Li+Stability of (2)Since desolvation energy is reduced, co-intercalation of the solvent can be effectively suppressed. In addition, the high-concentration lithium salt electrolyte can passivate an aluminum foil, so that the positive electrode material and the current collector can be kept in good contact, and the cycle service life of the lithium ion battery is prolonged.
According to the embodiment of the application, under the combined action of the organic solvent of the carboxylic ester compound, the cyclic carbonate or/and sulfonate film-forming agent and the high-concentration lithium salt, the ionic conductivity of the electrolyte can be improved, the SEI film and the charge transfer resistance can be reduced, the stability of electrode circulation can be enhanced, and the battery has a good cycle service life.
In some embodiments, the carboxylate based compound comprises one or more of methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, and methyl butyrate.
According to the embodiment of the application, the carboxylic ester compound is in a liquid state at normal temperature, wherein methyl formate, ethyl formate, methyl acetate and ethyl acetate have lower melting points and lower viscosity, methyl propionate, ethyl propionate, propyl propionate and methyl butyrate have lower melting points, and the carboxylic ester compound is used as an organic solvent to ensure that the electrolyte has higher ionic conductivity at low temperature.
In some embodiments, the organic solvent is 70 to 90% by volume based on the total volume of the electrolyte.
Preferably, the volume ratio of the organic solvent is 75-90%.
More preferably, the organic solvent accounts for 80-90% of the total volume of the composition.
According to the embodiment of the application, due to the difference of structures of the carboxylic ester compound and the conventional carbonate compound, the electrochemical stability of the carboxylic ester compound is poor, an oxidation-reduction reaction is easy to occur in the battery cycling process, and the cycle life of the battery is difficult to ensure, so that the carboxylic ester compound is used as a solvent and is added into an electrolyte in a proper amount. The volume ratio of the carboxylic ester organic solvent not only can reduce the melting point and viscosity of the electrolyte and improve the ionic conductivity of the electrolyte, but also can play a role together with the added film-forming agent and lithium salt so as to improve the cycling stability of the battery.
If the volume ratio of the carboxylic ester compound is lower than 70%, the volume of the film forming agent needs to be correspondingly increased, so that the reduction of the overall viscosity of the electrolyte and the improvement of the ionic conductivity are not facilitated, and the dissolution of high-concentration lithium salt is also not facilitated.
In some embodiments, the cyclic carbonate-based compound includes one or more of fluoroethylene carbonate, ethylene carbonate, vinylene carbonate.
In some embodiments, the sulfonate compound includes at least one of methanesulfonic acid-2-propyn-1-ol and 1, 3-propane sultone.
According to the embodiments of the present application, the cyclic carbonate compound refers to a carbonate compound having atoms in a cyclic arrangement in a molecule, and has a high dielectric constant; the sulfonate compound is a compound with a general formula R1SO2OR2The compound of (1). The cyclic carbonate compound and the sulfonate compound have high reaction activity, can react reduction reaction on the surface of the negative electrode of the battery to participate in the formation of an SEI film, further can improve the composition and structure of the SEI film, improve the mechanical property of the SEI film, prevent the reduction reaction of electrolyte on the surface of the negative electrode and the deposition of transition metal, stabilize the structure of a negative electrode material, and effectively inhibit the increase of internal resistance of the battery in the circulation process.
Furthermore, the sulfonate compound can also effectively inhibit oxidation reaction in a system, and plays a role in protecting the positive electrode. The film-forming agent is added into the electrolyte, so that the discharge platform of the battery can be obviously improved, and the cycle performance and the low-temperature discharge performance of the battery are improved.
In some embodiments, the film forming agent is 10-30% by volume based on the total volume of the electrolyte.
Preferably, the volume ratio of the film forming agent is 10-25%.
Further preferably, the volume ratio of the film forming agent is 10-20%.
According to the embodiment of the application, the addition amount of the film forming agent in the electrolyte is too large, so that the SEI film is too thick and the impedance is too large, and the performance of the battery is deteriorated; and too few film agents are not favorable for the formation of SEI film. When the volume percentage of the film forming agent in the application is 10-30%, an SEI film formed on the interface of the negative electrolyte is firm and thin, so that the stability of electrode circulation is ensured, and the transmission distance of lithium ions in the SEI film is shortened.
In some embodiments, the lithium salt comprises one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethanesulfonylimide, and lithium bistrifluorosulfonylimide.
Preferably, the lithium salt is lithium hexafluorophosphate or a mixture of lithium hexafluorophosphate with other lithium salts.
According to the embodiment of the application, the lithium salts with different components and proportions can be added to exert the synergistic effect among multiple lithium salts, and the component proportion of the SEI film is improved to be beneficial to Li+The electrolyte has good low-temperature performance by conduction, so that the rate capability, the cycle performance, the safety performance and the overcharge resistance of the lithium ion battery are improved. In addition, the addition of lithium salts may also facilitate Li+Thereby increasing the carrier concentration in the electrolyte and improving the conductivity of the electrolyte.
In some embodiments, the lithium salt has a molar concentration of 2 to 3 mol/L.
The lithium salt with the concentration is easy to dissolve in the electrolyte, and can promote the surface of the negative electrode to form a compact and firm SEI film, inhibit the co-intercalation of the solvent and achieve the effect of prolonging the cycle life of the lithium ion battery.
According to the embodiment of the application, the stability of the electrolyte can be further improved by regulating the types and the contents of the organic solvent, the film forming agent and the lithium salt to enable the organic solvent, the film forming agent and the lithium salt to exert a synergistic effect. In addition, the preparation method of the lithium ion battery electrolyte is simple, the existing process can be well compatible, and the prepared lithium ion battery electrolyte has good performance in a low-temperature environment and extremely has large-scale application potential.
Lithium ion battery
Embodiments of a further aspect of the present application provide a lithium ion battery, including the above lithium ion battery electrolyte.
According to the embodiment of the invention, the positive electrode used in the lithium ion battery can be lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate; the negative electrode used in the lithium ion battery may be graphite.
According to the lithium ion battery of the embodiment of the application, the lithium ion battery electrolyte comprises the lithium ion battery electrolyte in any embodiment of the first aspect, so that the lithium ion battery has good cycle life and capacity retention rate under a low-temperature environment. The lithium ion battery provided by the embodiment of the application can be applied to energy storage power systems such as hydraulic power, firepower, wind power and solar power stations in a low-temperature environment, and a plurality of fields such as electric tools, military equipment and aerospace.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking ethyl acetate: uniformly mixing a solution of fluoroethylene carbonate (in a volume ratio of 90: 10) to obtain an electrolyte solvent; adding a certain mass of lithium hexafluorophosphate into the electrolyte solvent to ensure that the concentration of the lithium hexafluorophosphate in the electrolyte is 3.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
And assembling the lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium manganate positive electrode and a graphite negative electrode into the button type lithium ion battery.
The lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium aluminate anode and a graphite cathode are assembled into a soft package lithium ion battery.
Example 2
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking methyl formate: ethyl acetate: uniformly mixing a solution of fluoroethylene carbonate (40: 40:20 by volume) to obtain an electrolyte solvent; a mixed lithium salt of lithium hexafluorophosphate and lithium dioxalate borate (mass ratio: 9:1) was added to the electrolyte solvent so that the concentration thereof in the electrolyte was 3.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
And assembling the lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium manganate positive electrode and a graphite negative electrode into a soft package lithium ion battery.
Example 3
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking methyl formate: methyl acetate: fluoroethylene carbonate: uniformly mixing vinylene carbonate solution 40:50:8:2 (volume ratio) to obtain an electrolyte solvent; adding lithium hexafluorophosphate to the electrolyte solvent: lithium bistrifluoromethanesulfonylimide as a mixed lithium salt in a ratio of 1:1 (mass ratio) so that the concentration thereof in the electrolyte solution is 2.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
And assembling the lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium manganate positive electrode and a graphite negative electrode into a soft package lithium ion battery.
Example 4
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking methyl acetate: methyl propionate: fluoroethylene carbonate: uniformly mixing a solution of 1, 3-propane sultone in a volume ratio of 60:30:7:3 to obtain an electrolyte solvent; adding lithium hexafluorophosphate to the electrolyte solvent: lithium bis (fluorosulfonyl) imide (1: 1) mixed lithium salt in a concentration of 3.0mol L in the electrolyte solution-1And fully dissolving to obtain the lithium ion battery electrolyte.
And assembling the lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium manganate positive electrode and a graphite negative electrode into a soft package lithium ion battery.
Example 5
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking butyric acid methyl ester: methyl propionate: fluoroethylene carbonate: uniformly mixing a solution of 1, 3-propane sultone in a volume ratio of 50:40:8:2 to obtain an electrolyte solvent; adding lithium hexafluorophosphate to the electrolyte solvent: lithium bis (fluorosulfonyl) imide (lithium salt) mixed in a mass ratio of 1:1 in an electrolyte solution at a concentration of 4.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
And assembling the lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium manganate positive electrode and a graphite negative electrode into a soft package lithium ion battery.
Example 6
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking ethyl acetate: methyl propionate: fluoroethylene carbonate: uniformly mixing vinylene carbonate solution with the volume ratio of 70:20:8:2 to obtain an electrolyte solvent; adding lithium hexafluorophosphate to the electrolyte solvent: lithium salt mixture of 1:1 (mass ratio) of lithium bis (fluorosulfonyl) imide, so that the concentration of lithium bis (fluorosulfonyl) imide in the electrolyte solution was 3.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
The lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium aluminate anode and a graphite cathode are assembled into a soft package lithium ion battery.
Example 7
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking ethyl acetate: uniformly mixing a solution of fluoroethylene carbonate (in a volume ratio of 90: 10) to obtain an electrolyte solvent; adding a certain mass of lithium hexafluorophosphate into the electrolyte solvent to ensure that the concentration of the lithium hexafluorophosphate in the electrolyte is 3.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
The lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium aluminate anode and a graphite cathode are assembled into a soft package lithium ion battery.
Example 8
The preparation method of the lithium ion battery electrolyte provided by the embodiment comprises the following steps: taking ethyl acetate: methyl propionate: fluoroethylene carbonate: uniformly mixing a solution of 1, 3-propane sultone in a volume ratio of 50:40:7:3 to obtain an electrolyte solvent; adding to the electrolyte solventLithium hexafluorophosphate: lithium salt mixture of lithium bistrifluoromethanesulfonylimide, the concentration of which in the electrolyte is 2.0mol L-1And fully dissolving to obtain the lithium ion battery electrolyte.
The lithium ion battery electrolyte in the embodiment, a nickel cobalt lithium aluminate anode and a graphite cathode are assembled into a soft package lithium ion battery.
Test section
The lithium ion batteries of the above examples 1 to 8 were tested at a certain temperature and a certain rate, and the results of the tests on the capacity retention rate of the lithium ion batteries are shown in table 1 below. Specifically, the cell was first formed at 25 ℃ at room temperature, i.e., the cell was charged and discharged at 0.1 ℃ for 3 cycles with constant current. After the formation was complete, the cell was charged and discharged at a constant current of 0.2C or 0.5C at low temperature, and the first cycle discharge capacity at low temperature was recorded. After cycling for X cycles in the above manner, the discharge capacity at the X-th cycle at low temperature was recorded.
In this test, the capacity retention (%) after the lithium ion battery was cycled X times was equal to the discharge capacity at the X-th cycle/the discharge capacity at the first cycle × 100%.
Table 1: results of Performance test of examples 1 to 8
According to the performance test results, the lithium ion batteries containing the electrolytes of examples 1 to 8 have good capacity retention rate. In conclusion, when the carboxylic ester compound is used as the organic solvent in the electrolyte, the good ionic conductivity of the electrolyte system at low temperature can be ensured; by adding the ester film-forming agent and the high-concentration lithium salt, a firm and thin solid electrolyte interface film can be formed on the surface of the negative electrode, and the resistance of an SEI film and charge transfer is reduced, so that the lithium ion battery still has high capacity retention rate after being cycled for many times in a low-temperature environment.
While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (9)
1. The lithium ion battery electrolyte comprises an organic solvent, a film forming agent and a lithium salt, and is characterized in that,
the organic solvent comprises a carboxylic ester compound;
the film forming agent comprises a cyclic carbonate compound or/and a sulfonate compound;
the molar concentration of the lithium salt is 2-4 mol/L.
2. The lithium ion battery electrolyte of claim 1 wherein the carboxylate compound comprises one or more of methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl propionate, and methyl butyrate.
3. The lithium ion battery electrolyte of claim 1, wherein the organic solvent is present in an amount of 70 to 90% by volume, based on the total volume of the electrolyte.
4. The lithium ion battery electrolyte of claim 1 wherein the cyclic carbonate based compound comprises one or more of fluoroethylene carbonate, ethylene carbonate, vinylene carbonate.
5. The lithium ion battery electrolyte of claim 1 wherein the sulfonate compound comprises at least one of methanesulfonic acid-2-propyn-1-ol and 1, 3-propanesultone.
6. The lithium ion battery electrolyte of claim 1, wherein the film-forming agent is present in an amount of 10 to 30% by volume, based on the total volume of the electrolyte.
7. The lithium ion battery electrolyte of claim 1 wherein the lithium salt comprises one or more of lithium hexafluorophosphate, lithium dioxalate borate, lithium bistrifluoromethanesulfonylimide, and lithium bistrifylsulfonylimide.
8. The lithium ion battery electrolyte of claim 1 wherein the lithium salt has a molar concentration of 2 to 3 mol/L.
9. A lithium ion battery comprising the lithium ion battery electrolyte according to any one of claims 1 to 8.
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