CN109768319B - Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same - Google Patents
Non-aqueous electrolyte for lithium ion battery and lithium ion battery using same Download PDFInfo
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- CN109768319B CN109768319B CN201711099724.6A CN201711099724A CN109768319B CN 109768319 B CN109768319 B CN 109768319B CN 201711099724 A CN201711099724 A CN 201711099724A CN 109768319 B CN109768319 B CN 109768319B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 41
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 17
- -1 cyano-substituted oxygen Chemical class 0.000 claims description 16
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 11
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052712 strontium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 5
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 4
- DSMUTQTWFHVVGQ-UHFFFAOYSA-N 4,5-difluoro-1,3-dioxolan-2-one Chemical compound FC1OC(=O)OC1F DSMUTQTWFHVVGQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910011297 LiCox Inorganic materials 0.000 claims description 3
- 229910013100 LiNix Inorganic materials 0.000 claims description 3
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 3
- 229910015818 MPO4 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011149 active material Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- LEGITHRSIRNTQV-UHFFFAOYSA-N carbonic acid;3,3,3-trifluoroprop-1-ene Chemical compound OC(O)=O.FC(F)(F)C=C LEGITHRSIRNTQV-UHFFFAOYSA-N 0.000 claims description 3
- SVTMLGIQJHGGFK-UHFFFAOYSA-N carbonic acid;propa-1,2-diene Chemical compound C=C=C.OC(O)=O SVTMLGIQJHGGFK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 150000008282 halocarbons Chemical group 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 30
- 238000002360 preparation method Methods 0.000 description 25
- 238000012360 testing method Methods 0.000 description 20
- 229940125904 compound 1 Drugs 0.000 description 19
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 12
- 229910021383 artificial graphite Inorganic materials 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 229910012820 LiCoO Inorganic materials 0.000 description 6
- 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 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000002161 passivation Methods 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- 150000005678 chain carbonates Chemical class 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- 239000011356 non-aqueous organic solvent Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 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
- 230000000996 additive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
Abstract
Non-aqueous electrolyte for lithium ion battery and lithium ion battery using sameThe electrolyte comprises a compound selected from compounds represented by formula 1, wherein R1、R2、R3、R4、R5、R6Each independently selected from hydrogen, fluorine, cyano or a group containing 1 to 5 carbon atoms; r is a group with the carbon number not more than 10, and the R contains 1 oxygen atom or 1 nitrogen atom. The non-aqueous electrolyte can improve the high-temperature storage and cycle performance of the lithium ion battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium ion battery non-aqueous electrolyte and a lithium ion battery using the same.
Background
Lithium ion batteries have been developed in the field of portable electronic products due to their high operating voltage, high safety, long life, no memory effect, and the like. With the development of new energy automobiles, the lithium ion battery has a huge application prospect in a power supply system for the new energy automobiles.
In a nonaqueous electrolyte lithium ion battery, a nonaqueous electrolyte is a key factor affecting high and low temperature performance of the battery, and particularly, an additive in the nonaqueous electrolyte is particularly important for exerting the high and low temperature performance of the battery. During the initial charging process of the lithium ion battery, lithium ions in the battery anode material are extracted and are inserted into the carbon cathode through electrolyte. Due to its high reactivity, the electrolyte reacts on the carbon negative electrode surface to produce Li2CO3And LiO, LiOH, etc., to form a passivation film on the surface of the negative electrode, which is referred to as a solid electrolyte interface film (SEI). At the initial chargingThe SEI film formed in the electric process not only prevents the electrolyte from being further decomposed on the surface of the carbon negative electrode, but also plays a role of lithium ion tunneling and only allows lithium ions to pass through. Therefore, the SEI film determines the performance of the lithium ion battery.
In order to improve various performances of the lithium ion battery, many researchers add different negative electrode film-forming additives (such as vinylene carbonate, fluoroethylene carbonate and ethylene carbonate) to the electrolyte to improve the quality of the SEI film, thereby improving various performances of the battery. For example, japanese patent application laid-open No. 2000-123867 proposes to improve battery characteristics by adding vinylene carbonate to an electrolyte. The vinylene carbonate can perform a reduction decomposition reaction on the surface of the negative electrode in preference to solvent molecules, and can form a passive film on the surface of the negative electrode to prevent the electrolyte from being further decomposed on the surface of the electrode, so that the cycle performance of the battery is improved. However, after the vinylene carbonate is added, the battery is easy to generate gas in the process of high-temperature storage, so that the battery is swelled. In addition, the passive film formed by vinylene carbonate has high impedance, and particularly under low-temperature conditions, lithium precipitation easily occurs in low-temperature charging, so that the safety of the battery is influenced. The fluoroethylene carbonate can also form a passive film on the surface of the negative electrode to improve the cycle performance of the battery, and the formed passive film has lower impedance and can improve the low-temperature discharge performance of the battery. However, the fluoroethylene carbonate generates more gas during high-temperature storage, and the high-temperature storage performance of the battery is obviously reduced.
Disclosure of Invention
The invention provides a lithium ion battery non-aqueous electrolyte capable of improving high-temperature storage and cycle performance of a battery, and further provides a lithium ion battery comprising the lithium ion battery non-aqueous electrolyte.
According to a first aspect, an embodiment provides a lithium ion battery nonaqueous electrolyte comprising a compound selected from the group consisting of compounds represented by formula 1,
wherein,R1、R2、R3、R4、R5、R6each independently selected from hydrogen, fluorine, cyano or a group containing 1 to 5 carbon atoms; r is a group with the carbon number not more than 10, and the R contains 1 oxygen atom or 1 nitrogen atom.
Further, the content of the compound represented by the structural formula 1 is 0.1% -10% by taking the total weight of the electrolyte as a reference.
Further, the above-mentioned group having 1 to 5 carbon atoms is selected from a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, a cyano-substituted hydrocarbon group or a cyano-substituted oxygen-containing hydrocarbon group.
Further, the above R1、R2、R3、R4、R5、R6Each independently selected from hydrogen, fluoro, cyano, methyl, ethyl, trimethylsiloxy, trifluoromethyl.
Further, R is selected from the group consisting of groups represented by structural formula 2 or structural formula 3:
structural formula 2:
wherein R is7、R8Each independently selected from hydrocarbyl groups with 1-5 carbon atoms, and m is an integer of 1-3;
structural formula 3:
wherein R is9、R10、R11Each independently selected from hydrocarbyl groups having 1 to 5 carbon atoms.
Further, the compound represented by the above structural formula 1 is selected from the following compounds:
The electrolyte solution further includes one or more of unsaturated cyclic carbonate, fluorinated cyclic carbonate, cyclic sultone, and cyclic sulfate.
Further, the unsaturated cyclic carbonate includes at least one of vinylene carbonate, ethylene carbonate, and methylene ethylene carbonate.
Further, the fluorinated cyclic carbonate includes at least one of fluoroethylene carbonate, trifluoromethyl ethylene carbonate, and difluoroethylene carbonate.
Further, the cyclic sultone may include at least one of 1, 3-propane sultone, 1, 4-butane sultone, and propenyl-1, 3-sultone.
Further, the cyclic sulfate includes at least one of vinyl sulfate and 4-methyl vinyl sulfate.
Further, the electrolyte includes a nonaqueous organic solvent and a lithium salt. The non-aqueous organic solvent is a mixture of cyclic carbonate and chain carbonate, the cyclic carbonate is one or more than two of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain carbonate is one or more than two of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
According to a second aspect, an embodiment provides a lithium ion battery comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, and further comprising the lithium ion battery nonaqueous electrolyte of the first aspect.
Further, the active material of the positive electrode is: LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、Liz’MPO4Wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than or equal to 0 and less than or equal to 1, 0<x 'is not less than 1, x is not less than 0.3 and not more than 0.6, y' is not less than 0.01 and not more than 0.2, L 'is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, z' is not less than 0.5 and not more than 1, and M is at least one of Fe, Mn and Co.
The lithium ion battery non-aqueous electrolyte contains the compound shown in the structural formula 1, during the first charging process, the compound shown in the structural formula 1 can perform a reduction decomposition reaction in preference to solvent molecules, a reaction product forms a layer of passivation film on the surface of an electrode, and the passivation film can inhibit the further decomposition of the solvent molecules. The formed passivation film can effectively prevent solvent molecules and lithium salt molecules from being further decomposed, so that high-impedance LiF components in the passivation film are less, the low-temperature performance is favorably improved, and meanwhile, the passivation film is favorable for lithium ions to pass through, so that the high-temperature storage and cycle performance of the battery can be obviously improved.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
One of the keys of the non-aqueous electrolyte of the lithium ion battery is that the non-aqueous electrolyte contains a compound shown in a structural formula 1, wherein R is1、R2、R3、R4、R5、R6Each independently selected from hydrogen, fluorine, cyano or a group containing 1 to 5 carbon atoms; r is a group with the carbon number not more than 10, and the R contains 1 oxygen atom or 1 nitrogen atom.
R1、R2、R3、R4、R5、R6Each independently selected from hydrogen, fluorine, cyano or a group containing 1 to 5 carbon atoms, wherein the group containing 1 to 5 carbon atoms may be selected from a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, a cyano-substituted hydrocarbon group or a cyano-substituted oxygen-containing hydrocarbon group.
R in the compound shown in the structural formula 11、R2、R3、R4、R5、R6Examples that may be selected, which may include, typically but not limited to: hydrogen, fluorine, cyano, methyl, ethyl, trimethylsiloxy, trifluoromethyl.
R in the compound shown in the structural formula 1 is a group with no more than 10 carbon atoms, and the R contains 1 oxygen atom or 1 nitrogen atom, preferably, the R is selected from the groups shown in structural formulas 2 and 3:
wherein R is7、R8Each independently selected from hydrocarbyl groups with 1-5 carbon atoms, and m is an integer of 1-3;
wherein R is9、R10、R11Each independently selected from hydrocarbyl groups having 1 to 5 carbon atoms.
Exemplary compounds among the compounds represented by structure 1 are shown in table 1, but are not limited thereto.
TABLE 1
Theoretically, the effect described in the present invention can be produced by adding the compound represented by the formula 1 (taking into account high-temperature storage and cycle of the battery), and it is understood that the effect is weak when the content is low, and the content of the compound represented by the formula 1 is preferably 0.1% or more with respect to the total mass of the nonaqueous electrolytic solution. In addition, from the viewpoint of the overall performance of the electrolyte, it is more preferable that the content of the compound represented by formula 1 is 10% or less with respect to the total mass of the nonaqueous electrolyte. Specifically, the content of the compound represented by formula 1 may be 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.4%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, 10%.
The lithium ion battery nonaqueous electrolyte solution of the present invention may further contain one or more other additives, for example, one or more of unsaturated cyclic carbonate, fluorinated cyclic carbonate, cyclic sultone, and cyclic sulfate. The additives can form a more stable SEI film on the surface of an electrode, so that the cycle performance of the lithium ion battery is improved. These additives may be added in amounts generally added in the art, for example, in the range of 0.1% to 10%, preferably 1% to 5%, more preferably 3% to 5%, relative to the total mass of the electrolyte.
Wherein the unsaturated cyclic carbonate can be at least one of vinylene carbonate (CAS: 872-36-6), ethylene carbonate (CAS: 4427-96-7) and methylene ethylene carbonate (CAS: 124222-05-5); the fluorinated cyclic carbonate can be at least one of fluoroethylene carbonate (CAS: 114435-02-8), trifluoromethyl ethylene carbonate (CAS: 167951-80-6) and difluoroethylene carbonate (CAS: 311810-76-1); the cyclic sultone can be at least one of 1, 3-propane sultone (CAS: 1120-71-4), 1, 4-butane sultone (CAS: 1633-83-6) and propenyl-1, 3-sultone (CAS: 21806-61-1); the cyclic sulfate may be at least one of vinyl sulfate (CAS: 1072-53-3) and 4-methyl vinyl sulfate (CAS: 5689-83-8).
It has been found that the compound represented by formula 1 of the present invention, when used in combination with the above-mentioned other additives, can achieve superior effects to those achieved when they are used alone, and it is presumed that there is a synergistic effect between them, i.e., the compound represented by formula 1 and the other additives cooperate to improve the high-temperature storage and cycle properties of the battery.
In the embodiment of the present invention, the nonaqueous electrolytic solution contains a nonaqueous organic solvent and a lithium salt, and the content and specific substance of the nonaqueous organic solvent and the lithium salt may be conventional, and there is no particular limitation in the present invention.
The non-aqueous organic solvent can be a mixture of cyclic carbonate and chain carbonate, the cyclic carbonate can be one or more than two of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain carbonate can be one or more than two of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate. The mixed solution of the cyclic carbonate organic solvent with high dielectric constant and the chain carbonate organic solvent with low viscosity is used as the solvent of the lithium ion battery electrolyte, so that the mixed solution of the organic solvent has high ionic conductivity, high dielectric constant and low viscosity.
In a preferred embodiment of the present invention, the lithium salt may be selected from LiPF6、LiBF4And the like.
One embodiment of the invention provides a lithium ion battery, which comprises a positive electrode, a negative electrode and a diaphragm arranged between the positive electrode and the negative electrode, and also comprises the lithium ion battery non-aqueous electrolyte.
In a preferred embodiment of the present invention, the active material of the positive electrode is: LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、Liz’MPO4Wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than or equal to 0 and less than or equal to 1, 0<x 'is not less than 1, x is not less than 0.3 and not more than 0.6, y' is not less than 0.01 and not more than 0.2, L 'is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, z' is not less than 0.5 and not more than 1, and M is at least one of Fe, Mn and Co.
The present invention is described in detail below with reference to specific examples. It should be understood that these examples are illustrative only and are not to be construed as limiting the scope of the invention.
Example 1
The preparation method of the lithium ion battery in this embodiment and other embodiments includes the steps of preparing an electrolyte, preparing a positive plate, preparing a negative plate, preparing a battery core, and injecting and forming the battery core; the performance tests of the lithium ion batteries of the embodiment and other embodiments include a high-temperature cycle performance test and a 60 ℃ high-temperature storage performance test, which are specifically as follows:
1) preparation of the electrolyte
Ethylene Carbonate (EC), diethyl carbonate (DEC) and Ethyl Methyl Carbonate (EMC) were mixed in a mass ratio of EC: DEC: EMC ═ 1:1:1, and then lithium hexafluorophosphate (LiPF) was added6) To a molar concentration of 1 mol/L. As shown in table 2, based on the total weight of the nonaqueous electrolytic solution taken as 100%, 1% of compound 1 was added based on the total weight of the electrolytic solution (compound 1 and compound 2 … … indicated in the examples refer to the corresponding numbers listed in table 1, and the same applies to the following examples).
2) Preparation of Positive plate
A positive electrode active material lithium nickel cobalt manganese oxide (LiNi) was mixed in a mass ratio of 93:4:30.5Co0.2Mn0.3O2) Or lithium cobaltate (LiCoO)2) (other examples), conductive carbon black Super-P, and a binder polyvinylidene fluoride (PVDF), which were then dispersed in N-methyl-2-pyrrolidone (NMP), to obtain a positive electrode slurry. And uniformly coating the slurry on two sides of the aluminum foil, drying, rolling and vacuum drying, and welding an aluminum outgoing line by using an ultrasonic welding machine to obtain the positive plate, wherein the thickness of the positive plate is 120-.
3) Preparation of negative plate
Mixing artificial graphite serving as a negative electrode active material, conductive carbon black Super-P, Styrene Butadiene Rubber (SBR) serving as a binder and carboxymethyl cellulose (CMC) according to a mass ratio of 94:1:2.5:2.5, and dispersing the materials in deionized water to obtain negative electrode slurry. Coating the slurry on two sides of the copper foil, drying, rolling and vacuum drying, and welding a nickel outgoing line by using an ultrasonic welding machine to obtain a negative plate, wherein the thickness of the negative plate is 120-150 mu m.
4) Preparation of cell
And placing three layers of isolating films with the thickness of 20 mu m between the positive plate and the negative plate, then winding the sandwich structure consisting of the positive plate, the negative plate and the isolating films, flattening the wound body, then placing the wound body into an aluminum foil packaging bag, and baking for 28 hours in vacuum at 85 ℃ to obtain the battery cell to be injected with liquid.
5) Liquid injection and formation of battery core
And (3) in a glove box with the dew point controlled below-40 ℃, injecting the prepared electrolyte into the battery cell, carrying out vacuum packaging, and standing for 24 hours. Then the first charge is normalized according to the following steps: charging at 0.05C for 180min, charging at 0.2C to 3.95V, vacuum sealing again, and further charging at 0.2C to 4.2V (LiNi)0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.4V (LiCoO)2Artificial graphite battery), standing at room temperature for 24hr, and discharging to 3.0V at constant current of 0.2C.
6) High temperature cycle performance test
Charging the formed battery to 4.2V (LiNi) at 45 ℃ with a constant current and a constant voltage of 1C0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.4V (LiCoO)2Artificial graphite cell) to a current of 0.01C and then discharged to 3.0V with a constant current of 1C. After N cycles of such charge/discharge, the capacity retention rate after the Nth cycle was calculated to evaluate the high-temperature cycle performance.
The calculation formula of the capacity retention rate at 45 ℃ for 1C circulation N times is as follows:
the nth cycle capacity retention (%) was (nth cycle discharge capacity/first cycle discharge capacity) × 100%.
Example 1 the capacity retention test data for 500 cycles at 45 ℃ and 1C are shown in table 2.
7)60 ℃ high temperature storage Property test
Charging the formed battery to 4.2V (LiNi) at room temperature by using a 1C constant current and a constant voltage0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.4V (LiCoO)2Artificial graphite battery) until the current is 0.01C, and discharging with 1C constant current until the current reaches3.0V, measuring the initial discharge capacity of the battery, and charging to 4.2V (LiNi) with 1C constant current and constant voltage0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.4V (LiCoO)2Artificial graphite battery) with a cutoff current of 0.01C, measuring the initial thickness of the battery, then storing the battery at 60℃ for N days, measuring the thickness of the battery, then discharging to 3.0V at a constant current of 1C, measuring the retention capacity of the battery, and then charging to 4.2V (LiNi) at a constant current and a constant voltage of 1C0.5Co0.2Mn0.3O2Artificial graphite battery) or 4.4V (LiCoO)2Artificial graphite cell) was cut off to a current of 0.01C and then discharged to 3.0V with a constant current of 1C, and the recovery capacity was measured. The calculation formulas of the capacity retention rate, the capacity recovery rate and the thickness expansion rate are as follows:
battery capacity retention (%) — retention capacity/initial capacity × 100%;
battery capacity recovery (%) — recovery capacity/initial capacity × 100%;
the battery thickness swelling ratio (%) (thickness after N days-initial thickness)/initial thickness × 100%.
Example 1 the 30 day capacity retention, capacity recovery and thickness swell test data stored at 60 c are shown in table 2.
Example 2
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was replaced with 1% of Compound 2 in the preparation of the electrolyte in the same manner as in example 1.
Example 3
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was changed to 0.1% of Compound 1 in the preparation of the electrolyte in the same manner as in example 1.
Example 4
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was changed to 2% of Compound 1 in the preparation of the electrolyte in the same manner as in example 1.
Example 5
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was changed to 3% of Compound 1 in the preparation of the electrolyte in the same manner as in example 1.
Example 6
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was replaced with 5% of Compound 1 in the preparation of the electrolyte in the same manner as in example 1.
Example 7
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was changed to 10% of Compound 1 in the preparation of the electrolyte in the same manner as in example 1.
Example 8
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of vinylene carbonate was additionally added to the preparation of the electrolyte in the same manner as in example 1.
Example 9
As shown in Table 2, the high temperature cycle performance and the high temperature storage performance of the electrolyte were measured in the same manner as in example 1 except that 1% fluoroethylene carbonate was additionally added to the preparation of the electrolyte, and the data are shown in Table 2.
Example 10
As shown in Table 2, the high temperature cycle performance and the high temperature storage performance data obtained by the test are shown in Table 2, except that 1% of 1, 3-propane sultone was additionally added to the preparation of the electrolyte, which is the same as example 1.
Example 11
As shown in Table 2, the high temperature cycle performance and the high temperature storage performance of the electrolyte were measured in the same manner as in example 1 except that 1% of vinyl sulfate was additionally added to the preparation of the electrolyte, and the data are shown in Table 2.
Comparative example 1
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was not added to the electrolyte preparation in the same manner as in example 1.
Comparative example 2
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was replaced with 1% of vinylene carbonate in the preparation of the electrolyte in the same manner as in example 1.
Comparative example 3
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was replaced with 1% of fluoroethylene carbonate in the preparation of the electrolyte in the same manner as in example 1.
Comparative example 4
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was replaced with 1% of 1, 3-propane sultone in the preparation of the electrolyte in the same manner as in example 1.
Comparative example 5
As shown in Table 2, the high temperature cycle characteristics and the high temperature storage characteristics obtained by the test were as shown in Table 2, except that 1% of Compound 1 was replaced with 1% of vinyl sulfate in the preparation of the electrolyte in the same manner as in example 1.
Comparative example 6
As shown in Table 2, except that 1% of Compound 1 was changed to 1% of LiN (SO) in the preparation of the electrolyte2F)2Otherwise, the same data as in example 1 were obtained and the high temperature cycle performance and the high temperature storage performance were measured as shown in Table 2.
TABLE 2
Example 13
As shown in table 3, the data of the high temperature cycle performance and the high temperature storage performance obtained by the test are shown in table 3, which is the same as example 1 except that the lithium nickel cobalt manganese oxide was replaced with lithium cobaltate in the preparation of the positive electrode plate.
Example 14
As shown in table 3, the data of the high temperature cycle performance and the high temperature storage performance obtained by the test are shown in table 3, which is the same as example 2 except that the lithium nickel cobalt manganese oxide was replaced with lithium cobaltate in the preparation of the positive electrode plate.
Example 15
As shown in table 3, the data of the high temperature cycle performance and the high temperature storage performance obtained by the test are shown in table 3, which is the same as example 3 except that the lithium nickel cobalt manganese oxide was replaced with lithium cobaltate in the preparation of the positive electrode plate.
Comparative example 7
As shown in table 3, the data of the high temperature cycle performance and the high temperature storage performance obtained by the test are shown in table 3, which is the same as in comparative example 1 except that the lithium nickel cobalt manganese oxide was replaced with lithium cobaltate in the preparation of the positive electrode plate.
TABLE 3
From the results in tables 2 and 3, it can be seen that the addition of the compound shown in formula 1 can significantly improve the capacity retention rate of the lithium ion battery at 45 ℃ for 300 weeks at 1C cycle, and the capacity retention rate, capacity recovery rate and thickness expansion rate performance of the lithium ion battery stored at 60 ℃ for 14 days, no matter whether the cathode material is lithium nickel cobalt manganese oxide or lithium cobaltate.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. A lithium ion battery non-aqueous electrolyte is characterized by comprising a compound shown in a structural formula 1,
structural formula 1:
wherein R is1、R2、R3、R4、R5、R6Each independently selected from hydrogen, fluorine, cyano or a group containing 1 to 5 carbon atoms; r is a group with the carbon number not more than 10, and only 1 oxygen atom or 1 nitrogen atom is contained in the R.
2. The electrolyte of claim 1, wherein the compound of formula 1 is present in an amount of 0.1% to 10% based on the total weight of the electrolyte.
3. The electrolyte of claim 1, wherein the group having 1 to 5 carbon atoms is selected from a hydrocarbon group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group, a cyano-substituted hydrocarbon group, or a cyano-substituted oxygen-containing hydrocarbon group.
4. The electrolyte of claim 1, wherein R is1、R2、R3、R4、R5、R6Each independently selected from hydrogen, fluoro, cyano, methyl, ethyl, trimethylsiloxy, trifluoromethyl.
5. The electrolyte of claim 1, wherein R is selected from the group consisting of groups represented by structural formula 2 or structural formula 3:
structural formula 2:
wherein R is7、R8Each independently selected from hydrocarbyl groups with 1-5 carbon atoms, and m is 1;
structural formula 3:
wherein R is9、R10、R11Each independently selected from hydrocarbyl groups having 1 to 5 carbon atoms.
6. The electrolyte of claim 1, wherein the compound of formula 1 is selected from the group consisting of:
7. the electrolyte according to claim 1, wherein the electrolyte further comprises one or more of unsaturated cyclic carbonate, fluorinated cyclic carbonate, cyclic sultone, and cyclic sulfate.
8. The electrolyte of claim 7, wherein the unsaturated cyclic carbonate comprises at least one of vinylene carbonate, ethylene carbonate, and methylene ethylene carbonate;
the fluorinated cyclic carbonate comprises at least one of fluoroethylene carbonate, trifluoromethyl ethylene carbonate and difluoroethylene carbonate;
the cyclic sultone comprises at least one of 1, 3-propane sultone, 1, 4-butane sultone and propenyl-1, 3-sultone;
the cyclic sulfate includes at least one of vinyl sulfate and 4-methyl vinyl sulfate.
9. A lithium ion battery comprising a positive electrode, a negative electrode, and a separator interposed between the positive electrode and the negative electrode, characterized by further comprising the lithium ion battery nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. The lithium ion battery according to claim 9, wherein the active material of the positive electrode is: LiNixCoyMnzL(1-x-y-z)O2、LiCox’L(1-x’)O2、LiNix”L’y’Mn(2-x”-y’)O4、Liz’MPO4Wherein L is at least one of Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x + y + z is more than or equal to 0 and less than or equal to 1, 0<x 'is not less than 1, x is not less than 0.3 and not more than 0.6, y' is not less than 0.01 and not more than 0.2, L 'is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe, z' is not less than 0.5 and not more than 1, and M is at least one of Fe, Mn and Co.
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