CN110943252A - Electrolyte and lithium ion battery - Google Patents
Electrolyte and lithium ion battery Download PDFInfo
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- CN110943252A CN110943252A CN201811115489.1A CN201811115489A CN110943252A CN 110943252 A CN110943252 A CN 110943252A CN 201811115489 A CN201811115489 A CN 201811115489A CN 110943252 A CN110943252 A CN 110943252A
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- Prior art keywords
- electrolyte
- additive
- halogen
- lithium ion
- ion battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 79
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- 239000000654 additive Substances 0.000 claims abstract description 83
- 230000000996 additive effect Effects 0.000 claims abstract description 79
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 150000002367 halogens Chemical class 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000005486 organic electrolyte Substances 0.000 abstract 1
- 238000007599 discharging Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- -1 cyclic carbonate ester Chemical class 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 238000006864 oxidative decomposition reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 150000005678 chain carbonates Chemical class 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
- 238000001035 drying Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000003660 carbonate based solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
- 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)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to the field of energy storage materials, in particular to electrolyte and a battery using the electrolyte, the electrolyte comprises an organic solvent and electrolyte dissolved in the organic solvent, the electrolyte comprises an additive A and an additive B,
wherein R is1、R2、R3、R4And R5Each independently selected from halogen atom, halogen-containing C1～C12Alkyl, halogen-containing C1～C12Alkoxy, halogen-containing C2～C12Alkenyl, halogen-containing C2～C12Alkynyl, halogen-containing C6～C26Aryl and halogen-containing C4～C12Heterocyclic radicalAt least one of (1), R6Is a halogen-containing alkoxy radical, R7、R8And R9Are respectively C2～C10An alkyl group. The additive A and the additive B enable the lithium ion battery applying the electrolyte to form a good interfacial film on positive and negative electrode interfaces, and meanwhile, the interfacial film has low impedance, so that the low-temperature discharge performance and the high-rate charging performance of the lithium ion battery are improved.
Description
Technical Field
The application relates to the field of energy storage materials, in particular to electrolyte and a lithium ion battery using the electrolyte.
Background
Lithium ion batteries are widely used in daily life, such as notebook computers, mobile phones, digital cameras, and electric vehicles. At room temperature, the lithium ion battery has the advantages of long service life, low self-discharge rate, high specific energy density and the like. However, the conventional lithium ion battery has a problem that the capacity thereof is not restored to the original capacity at the room temperature even after the low-temperature cycle because of a large capacity fade at a low temperature. Therefore, the low-temperature discharge performance and the high-rate charge performance of the lithium ion battery limit the application of the lithium ion battery in extremely cold regions and under the requirement of high-power discharge.
In order to avoid the influence of the above factors on electronic devices or equipment using lithium ion batteries, how to improve the discharge performance and high-rate charging performance of lithium ion batteries in low temperature environments is a problem that needs to be solved urgently.
Disclosure of Invention
In view of the above, it is desirable to provide an electrolyte solution that can improve the high rate charging performance and low temperature discharging performance of a battery.
In addition, a lithium ion battery applying the electrolyte is also needed to be provided.
The object of the present application is to provide an electrolyte comprising a solvent, an electrolyte and an additive, which is characterized in that
Characterized in that the additives comprise an additive A and an additive B,
wherein R is1、R2、R3、R4And R5Each independently selected from halogen atom, halogen-containing C1～C12Alkyl, halogen-containing C1～C12Alkoxy, halogen-containing C2～C12Alkenyl, halogen-containing C2～C12Alkynyl, halogen-containing C6～C26Aryl and halogen-containing C4～C12At least one of heterocyclic radicals, R6Is a halogen-containing alkoxy radical, R7、R8And R9Are respectively C2～C10An alkyl group.
Another object of the present application is to provide a lithium ion battery, which includes a positive electrode plate, a negative electrode plate, a separator disposed between the positive electrode plate and the negative electrode plate, and the electrolyte of the first aspect.
The technical scheme of the application has at least the following beneficial effects:
the electrolyte contains the additive A and the additive B, so that a lithium ion battery applying the electrolyte forms a good interface film on a positive electrode interface and a negative electrode interface, and meanwhile, the interface film has low impedance, thereby being beneficial to improving the low-temperature discharge performance and the high-rate charging performance of the lithium ion battery.
Detailed Description
In order to make the object, technical solution and advantageous technical effects of the present invention clearer, the present invention is further described in detail with reference to the following embodiments. It should be understood that the examples described in this specification are for the purpose of illustration only and not for the purpose of limiting the application, and the formulations, proportions, etc. of the examples may be selected accordingly without materially affecting the results.
The electrolyte and the lithium ion battery according to the present application are described in detail below.
The invention provides an electrolyte applied to a lithium ion battery, which comprises a solvent, an electrolyte and an additive, and is characterized in that the additive comprises an additive A and an additive B,
wherein R is1、R2、R3、R4And R5Each independently selected from halogen atom, halogen-containing C1～C12Alkyl, halogen-containing C1～C12Alkoxy, halogen-containing C2～C12Alkenyl, halogen-containing C2～C12Alkynyl, halogen-containing C6～C26Aryl and halogen-containing C4～C12At least one of heterocyclic radicals, R6Is a halogen-containing alkoxy radical, R7、R8And R9Are respectively C2～C10An alkyl group.
When the electrolyte is applied to a lithium ion battery, an N ═ P double bond in the structure of the additive A and HF generated by the side reaction of the electrolyte generate electrophilic addition reaction, and further HF is removed, so that the corrosion of HF to a positive electrode interface is reduced, and the positive electrode interface is indirectly protected; the additive B takes part in an oxidation reaction in advance by trapping active oxygen at the cathode interface, and participates in film formation at the cathode interface to inhibit further generation of the active oxygen, thereby inhibiting oxidative decomposition of the electrolyte. When the electrolyte contains only the additive A, although the generation of active oxygen on the cathode interface can be inhibited, HF acid existing in the electrolyte can attack the cathode interface, so that the interface film is damaged, and the electrolyte is subjected to oxidative decomposition; if only the additive B is contained in the electrolyte solution, the generation of active oxygen cannot be suppressed, and the active oxygen also causes oxidative decomposition of the electrolyte solution. When the additive A and the additive B are combined, on one hand, the damage of HF to the interface film can be inhibited, on the other hand, the generation of active oxygen can be inhibited, and the oxidative decomposition of the electrolyte can be inhibited from the source. The electrolyte oxidation product is attached to the cathode interface, which generally causes the cathode interface impedance to be increased, and the additive A and the additive B are combined to indirectly reduce the cathode interface impedance by inhibiting the electrolyte oxidation decomposition, so that the lithium ions can be rapidly conducted, and the low-temperature discharge performance and the high-rate charging performance of the lithium ion battery can be improved.
In one embodiment of the present invention, the electrolyte has a free acid content of less than 50 ppm.
As an embodiment of the present invention, R in additive A1、R2、R3、R4And R5At least one of which is a fluorine atom. Preferably, R1、R2、R3、R4And R5Are all fluorine atoms. The reason why fluorine atoms are preferred among halogens is that fluorine elements have a large electronegativity, so that the upper part of a P atom has a negative charge, which facilitates H in free acid HF to attack the P atom, and the fluorine atoms have a small radius, which can reduce the steric hindrance of H attack. Therefore, when the side chain of the additive A contains F atoms, the additive A is favorable for capturing HF and reducing the corrosion of HF to a cathode interface, and the more the relative content of the F atoms in the additive A is, the stronger the adsorption effect on free acid HF in the electrolyte is, and the corrosion of HF acid to the cathode interface is favorably inhibited.
In the present embodiment, the content of the additive a in the electrolyte solution is 0.01% to 3% by mass, preferably 0.1% to 2% by mass. When the concentration is in the range, the additive A has strong adsorption effect on free acid HF, and is favorable for inhibiting corrosion of HF acid on a cathode interface; in addition, when the electrolyte is in this range, the conductivity of the electrolyte is also preferable.
In this embodiment, R in additive B7、R8And R9Each independently selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl or decyl. Preferably, R7、R8And R9Each independently selected from ethyl or propyl. R7、R8And R9When the methyl is adopted, the substance is gaseous at normal temperature and is not suitable for being used as an electrolyte additive, and when the alkyl chain is long, the molecular steric hindrance is large, so that the substance is not beneficial to capturing active oxygen. Preferred substituents are therefore ethyl or propyl.
In this embodiment, the additive B is at least one selected from tripropyl phosphite and triethyl phosphite.
In the present embodiment, the mass percentage content of the additive B in the electrolyte solution is preferably 0.01% to 1%, and more preferably 0.1% to 0.5%.
In the present embodiment, the mass (m2) ratio of the additive A (m1) to the additive B is 1. ltoreq. m1/m 2. ltoreq.2. When the content of the additive A is more than that of the additive B, the decomposition of the electrolyte can be effectively inhibited, and the deterioration of the interface impedance by the additive B can be inhibited; when the mass ratio of the additive A to the additive B is within 2 times, the viscosity of the electrolyte is not obviously increased, the conductivity of the electrolyte is higher, and the power performance of the electrolyte is excellent.
In other embodiments, the electrolyte may further include an additive C, which may be selected from, but not limited to, at least one of a compound of formula III, a compound of formula IV, and a compound of formula V,
wherein R is10May be, but is not limited to, C2～C12Alkenyl radical, R11And R12Each may be, but is not limited to, hydrogen, C1～C12Alkyl group, and the like. The additive C participates in the formation of an anode interface SEI film in the formation process, can inhibit the reduction and decomposition of electrolyte in the battery cell circulation process, reduces the anode interface impedance, can reduce the overall interface impedance of the battery cell by being combined with the additive A, B, is beneficial to the rapid movement of lithium ions, and further improves the low-temperature discharge performance and the high-rate charging performance of the lithium ion battery.
Preferably, the additive C comprises at least one of ethylene carbonate, lithium bis (fluorosulfonylimide) and vinyl sulfate.
Further preferably, the ratio of the mass of the additive C to the sum of the masses of the additive A and the additive B is 0.5 to 2.
In the present embodiment, the organic solvent includes at least one of a chain carbonate solvent, a cyclic carbonate solvent, a chain carboxylic acid ester solvent, γ -butyrolactone, and tetrahydrofuran. In the present embodiment, the chain carbonate-based solvent is at least one selected from, but not limited to, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, propyl methyl carbonate, and propyl ethyl carbonate. The cyclic carbonate ester solutionThe agent is selected from but not limited to vinylene carbonate
Propylene carbonate and ethylene carbonate
Propylene carbonate
And butylene carbonate, and the like. The chain carboxylic ester solvent is at least one selected from but not limited to methyl formate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate and the like.
In the present embodiment, the organic solvent is contained in the electrolyte in an amount of 65% to 85% by mass. The organic solvent still has good thermal stability and electrochemical stability at a high temperature and a high voltage, and can provide a stable electrochemical environment for the electrical property of a lithium ion battery with the voltage of more than or equal to 4.2V.
In the present embodiment, the electrolyte may be selected from, but not limited to, at least one of lithium hexafluorophosphate, lithium bis (trifluoromethyl) sulfonimide, lithium tetrafluoroborate, lithium trifluoromethanesulfonate, lithium hexafluoroarsenate, lithium bis (oxalato) borate, lithium perchlorate, and the like. Preferably, the electrolyte is lithium hexafluorophosphate.
In the present embodiment, the concentration of the electrolyte is 0.5mol/L to 1.5 mol/L. Preferably, the concentration of the electrolyte is 0.8mol/L to 1.2 mol/L.
The invention also provides a lithium ion battery applying the electrolyte, which further comprises other elements such as a positive electrode, an isolating membrane, a negative electrode and a shell. The case accommodates the positive electrode, the separator, the negative electrode, and the electrolyte.
The present invention will be specifically explained below with reference to a lithium ion battery.
Preparation of the electrolyte
The electrolyte was prepared in an argon-filled glove box having a water content of less than 10ppm and a low oxygen contentAt 1 ppm. The preparation of the electrolyte comprises the following steps: adding an additive A, an additive B and other proper additives (such as vinylene carbonate) into an organic solvent composed of Ethylene Carbonate (EC) and diethyl carbonate (DEC), and uniformly mixing, wherein the weight ratio of EC: DEC-30: 70; then adding LiPF slowly into the organic solvent6And dissolved to prepare an electrolyte of an embodiment, wherein the LiPF6The concentration of (2) is 1 mol/L.
The electrolyte of the comparative example was different from the electrolyte of the example in that: the electrolyte does not contain the additive A and the additive B or only contains one of the additive A and the additive B.
In this embodiment, the electrolyte of 15 examples is compared with the electrolyte of 3 comparative examples, and the substances and contents of the additives in the electrolytes of the examples and comparative examples are specifically shown in table 1.
TABLE 1
Preparation of positive plate
Reacting LiNi0.8Co0.1Mn0.1O2Adding carbon black and polyvinylidene fluoride (PVDF) into N-methyl pyrrolidone (NMP) and uniformly mixing to obtain positive electrode slurry, wherein the solid content of the positive electrode slurry is 50%, and LiNi is the mass ratio0.8Co0.1Mn0.1O2: carbon black: PVDF-8: 1: 1.
And coating the positive electrode slurry on a current collector aluminum foil, drying at 85 ℃, then carrying out cold pressing, slicing, cutting and slitting, and then carrying out vacuum drying at 85 ℃ for 4 hours to obtain the positive electrode plate.
Preparation of negative plate
Adding graphite, carbon black, a thickening agent CMC and Styrene Butadiene Rubber (SBR) into deionized water, and uniformly mixing to obtain negative electrode slurry, wherein the solid content of the negative electrode slurry is 30%, and the mass ratio of graphite: carbon black: CMC: SBR 80:15:3: 2.
And coating the negative electrode slurry on a current collector copper foil, drying at 85 ℃, cold-pressing, slicing, cutting into pieces, slitting, and vacuum-drying at 120 ℃ for 12 hours to obtain the negative electrode piece.
Assembly of lithium ion batteries
And the positive plate, an isolating membrane and the negative plate are sequentially stacked and wound to form a battery cell, the isolating membrane isolates the positive plate and the negative plate, tabs are welded on the battery cell, the battery cell is placed in a shell to form an intermediate, the electrolyte is respectively injected into the shell of the intermediate, and then subsequent processes such as packaging, standing and the like are carried out, so that the lithium ion batteries are correspondingly prepared and the capacity of each lithium ion battery is determined. Wherein, the isolating film is a polyethylene film with the thickness of 16 microns; the thickness of the lithium ion battery is 40mm, the width of the lithium ion battery is 60mm, and the length of the lithium ion battery is 140 mm.
And carrying out high-rate charging performance test and low-temperature discharging performance test on the lithium ion battery.
And (3) testing the high-rate charging performance:
at 25 ℃, 0.5C was charged to 4.2V, then 1C was discharged to 2.8V, and then the charge rate was adjusted to 5C in sequence, and the charge was cut off to 4.2V. Discharge to 2.8V at 1C, and the discharge capacity (C) at each time was recorded1、C2). The charge capacity retention ratio of 5C is ═ C2/C1×100％
And (3) testing low-temperature discharge performance:
charging the lithium ion battery to 4.2V at 1C at room temperature, then charging to 0.05C at a constant voltage of 4.2V, adjusting the ambient temperature to room temperature, discharging to 2.8V at 1C when the surface temperature of the battery reaches the room temperature, and recording the discharge capacity C0; charging the battery cell to 4.2V at 1C, charging the battery cell to 0.05C at constant voltage, adjusting the ambient temperature to-30 ℃, discharging the battery cell to 2.8V at 1C when the surface temperature of the battery cell is-30 ℃, recording the discharge capacity as C2, and keeping the discharge capacity retention rate of the battery cell as C at low temperature2/C1×100％
TABLE 2
As can be seen from table 2, the lithium ion batteries of examples 1 to 11 have better high rate charging performance and low temperature discharging performance compared to the lithium ion batteries of comparative examples 1 to 3, which indicates that the power performance of the electrolyte can be effectively improved by using the additive a and the additive B together. Furthermore, when the mass percentage of the additive A in the electrolyte is 0.01-3% and the mass percentage of the additive B in the electrolyte is 0.01-1%, the high-rate charging performance and the low-temperature discharging performance of the battery are better.
Compared with comparative example 2 without additive B, although additive A can capture HF and protect the cathode structure from being damaged to a certain extent, a better interface film is not formed on the cathode interface, and the electrolyte is difficult to inhibit the oxidative decomposition, so that the high-rate charging performance and the low-temperature discharging performance are inferior to those of example 3; in comparative example 3, the additive a was not contained, and the additive B could form a film on the cathode interface, but could not block the corrosion by HF, so that the corrosion of the cathode interface resulted in the oxidative decomposition of the electrolyte, and the decomposition product covered the interface, resulting in the increase of the impedance and the deterioration of the power performance of the electrolyte.
The high-rate charging capability and the low-temperature discharging capability of the embodiments 12 to 15 are both good, because the anode film-forming additive C is added on the basis of the combination of the additives a and B, the anode film-forming additive C can effectively inhibit the electrolyte from being reduced and decomposed at the anode, thereby avoiding the deterioration of the interface impedance of the battery cell anode by electrolyte byproducts, and improving the power performance of the electrolyte, so that the charging and discharging capability of the battery is stronger.
Therefore, the electrolyte containing the additive A and the additive B can improve the high-rate charging performance and the low-temperature discharging performance of the lithium ion battery, so that the comprehensive performance of the lithium ion battery is improved.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing specification. Therefore, the present application is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present application should fall within the scope of the claims of the present application. In addition, although specific terms are used herein, they are used in a descriptive sense only and not for purposes of limitation.
Claims (10)
1. An electrolyte solution, comprising a solvent, an electrolyte and an additive, wherein the additive comprises an additive A and an additive B, the additive A is at least one of compounds represented by formula I, and the additive B is at least one of compounds represented by formula II:
wherein R is1、R2、R3、R4And R5Each independently selected from halogen atom, halogen-containing C1～C12Alkyl, halogen-containing C1～C12Alkoxy, halogen-containing C2～C12Alkenyl, halogen-containing C2～C12Alkynyl, halogen-containing C6～C26Aryl and halogen-containing C4～C12At least one of heterocyclic radicals, R6Is a halogen-containing alkoxy radical, R7、R8And R9Are respectively C2～C10An alkyl group.
2. The electrolyte of claim 1, wherein R in the additive A is1、R2、R3、R4And R5At least one of them being a fluorine atom, preferably R1、R2、R3、R4And R5Are all fluorine atoms.
3. The electrolyte of claim 1, wherein the additive A is present in the electrolyte in an amount of 0.01 to 3% by weight, preferably 0.1 to 2% by weight.
4. The electrolyte of claim 1, wherein R in the additive B is7、R8And R9Each independently selected from ethyl, propyl, butyl, pentyl, hexyl, heptyl, nonyl or decyl, preferably, R is7、R8And R9Each independently selected from ethyl or propyl.
5. The electrolyte according to claim 1, wherein the additive B is present in the electrolyte in an amount of 0.01 to 1% by weight, preferably 0.1 to 0.5% by weight.
6. The electrolyte of any one of claims 1, 3 or 5, wherein the mass ratio of the additive A to the additive B is between 1 and 2.
7. The electrolyte of claim 1, further comprising an additive C comprising at least one of a compound of formula III, a compound of formula IV, and a compound of formula V,
wherein R is10Comprising C2～C12Alkenyl radical, R11And R12Each independently selected from hydrogen and C1～C12At least one of alkyl radicals, R13And R14Each independently selected from fluorine, fluorine substituted C1～C12At least one of alkyl groups of (a).
8. The electrolyte of claim 7, wherein the additive C is at least one of ethylene carbonate, lithium bis (pentafluoroethylsulfonimide) and vinyl sulfate.
9. The electrolyte of claim 7, wherein the ratio of the mass of the additive C to the sum of the masses of the additive A and the additive B is between 0.5 and 2.
10. A lithium ion battery comprising a positive electrode plate, a negative electrode plate, a separator disposed between the positive electrode plate and the negative electrode plate, and an electrolyte, wherein the electrolyte is the electrolyte according to any one of claims 1 to 9.
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