CN113809401B - Nonaqueous electrolyte for lithium ion battery and application thereof - Google Patents
Nonaqueous electrolyte for lithium ion battery and application thereof Download PDFInfo
- Publication number
- CN113809401B CN113809401B CN202111249776.3A CN202111249776A CN113809401B CN 113809401 B CN113809401 B CN 113809401B CN 202111249776 A CN202111249776 A CN 202111249776A CN 113809401 B CN113809401 B CN 113809401B
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium ion
- ion battery
- nonaqueous electrolyte
- additive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 141
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 99
- 239000000654 additive Substances 0.000 claims abstract description 88
- 150000001875 compounds Chemical class 0.000 claims abstract description 84
- 230000000996 additive effect Effects 0.000 claims abstract description 81
- -1 cyclic ester Chemical class 0.000 claims abstract description 58
- 239000002904 solvent Substances 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 33
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 40
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 32
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims description 26
- 159000000002 lithium salts Chemical class 0.000 claims description 26
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 24
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 24
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 24
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims description 21
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 5
- OQXNUCOGMMHHNA-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2,2-dioxide Chemical compound CC1COS(=O)(=O)O1 OQXNUCOGMMHHNA-UHFFFAOYSA-N 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 4
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 4
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 4
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910021382 natural graphite Inorganic materials 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 125000003342 alkenyl group Chemical group 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002156 mixing Methods 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IFDLFCDWOFLKEB-UHFFFAOYSA-N 2-methylbutylbenzene Chemical compound CCC(C)CC1=CC=CC=C1 IFDLFCDWOFLKEB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- SSBFISCARUPWGN-UHFFFAOYSA-N [Li].C(C(=O)F)(=O)F Chemical compound [Li].C(C(=O)F)(=O)F SSBFISCARUPWGN-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- VCZQFJFZMMALHB-UHFFFAOYSA-N tetraethylsilane Chemical compound CC[Si](CC)(CC)CC VCZQFJFZMMALHB-UHFFFAOYSA-N 0.000 description 3
- 239000002000 Electrolyte additive Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DGAHZYUYIUHURU-UHFFFAOYSA-N 1,2-bis(ethenyl)-3,4-diethylbenzene Chemical compound C(C)C1=C(C(=C(C=C1)C=C)C=C)CC DGAHZYUYIUHURU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 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
- 238000011049 filling Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a non-aqueous electrolyte of a lithium ion battery and application thereof. The lithium ion battery nonaqueous electrolyte comprises an electrolyte, a nonaqueous solvent and an additive, wherein the additive comprises a first compound and a cyclic ester additive. The first compound contains a plurality of electron-rich alkenyl substituent groups, while the network dimension of the polymer formed from the first compound additive plays an important role in lithium ion conduction. Due to the presence of multiolefin structures, the network structure formed by the polymers has different dimensions, thereby being able to influence the transport of lithium ions. The invention can inhibit the reaction between the electrolyte and the positive electrode under the high temperature state by utilizing the synergistic effect of the first compound and the cyclic ester additive, thereby improving the high temperature storage performance of the lithium ion battery.
Description
Technical Field
The invention belongs to the field of batteries, and particularly relates to a nonaqueous electrolyte for a lithium ion battery and application of the nonaqueous electrolyte.
Background
Compared with the traditional lead-acid battery, the lithium ion battery is used as a rechargeable battery, has the advantages of high energy density, small self-discharge, long cycle life and the like, and is widely applied to the fields of electric automobiles, smart grids, miniaturized electronic equipment and the like. At present, the use safety problem of the lithium ion battery is still an important factor for restricting the application development of the lithium ion battery.
The electrolyte of the lithium ion battery mostly adopts an organic solvent system, and when the charging current is large, the temperature of the battery system is increased, so that potential safety hazards such as expansion and gas production of the battery system are caused. In addition, in order to further increase the energy density of the lithium ion battery, researchers often use ternary cathode materials with high specific capacity and high reaction potential, and simultaneously, higher requirements are also put on the electrolyte. In summary, improving the stability of the electrolyte is an effective method for improving the safety of the lithium ion battery, for example, adding some film forming additives, conductive additives and multifunctional additives to the electrolyte can further improve the safety performance of the battery.
The electrolyte additive is used in an amount of only a small portion (typically less than 5 wt%) of the electrolyte in a lithium ion battery, but a suitable amount of additive is capable of forming a solid electrolyte interphase (Solid Electrolyte Interface, SEI) film on the surface of the negative and/or positive electrode. The SEI film can form a layer of protective film on the surfaces of the anode material and the cathode material, and avoid side reactions with electrolyte continuously. Among them, cyclic carbon-and sulfur-containing compounds are currently widely used electrolyte additives, such as vinylene carbonate and fluoroethylene carbonate, which are capable of better passivating graphite anodes and/or cathodes. However, the SEI film has problems of non-uniformity, damage and instability during recycling.
Based on the above considerations, it is desirable in the art to develop a lithium ion battery electrolyte that is capable of forming not only a stable and thin SEI film, but also improving the electrochemical performance of the battery at high temperatures.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a non-aqueous electrolyte for a lithium ion battery and application thereof. The invention provides the electrolyte which can inhibit the reaction between the electrolyte and the positive electrode at a high temperature state, and is used cooperatively with the cyclic ester additive to prepare the stable SEI film, thereby improving the high-temperature cycle performance of the lithium ion battery.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a lithium ion battery nonaqueous electrolyte comprising an electrolyte, a nonaqueous solvent, and an additive comprising a first compound having a structure represented by formula 1 and a cyclic ester additive:
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from a linear alkyl group of-ch=ch-X, C2 to C6 or a branched alkyl group of C2 to C6.
The X is selected from a linear alkyl group of-H, C to C6 or a branched alkyl group of C2 to C6.
The R is 1 、R 2 、R 3 And R is 4 At least one of which is selected from-ch=ch-X.
In the present invention, the first compound additive contains a plurality of electron-rich alkenyl substituent groups, while the network dimension of the polymer formed from the first compound additive plays an important role in lithium ion conduction. The network structure formed by the polymer has different sizes due to the presence of the multiolefin structure, so that the size of the ion channels formed by the network structure can influence the transmission of lithium ions. The number of nodes is used to define the lithium ion transmission channel formed by the polymerization of the first compound, for example: when the first compound contains only one vinyl group and oxidative polymerization occurs, the number of nodes of the compound is 1 for one structural repeating unit; the first compound contains two vinyl groups, the number of nodes of the compound is 2 for one structural repeat unit, and so on. In the present invention, when the number of nodes is too small, the polymer structure constituting the SEI film cannot form a dense protective film; and when the number of nodes is too large, efficient transmission of lithium ions is hindered. Therefore, the invention is regulated within the proper content range of the olefin additive, so that the number of the nodes is between 2 and 2.5, which is beneficial to improving the high-temperature storage performance of the lithium ion battery.
Preferably, the first compound includes a second compound having a structure shown in formula 2, a third compound having a structure shown in formula 3, a fourth compound having a structure shown in formula 4, and/or a fifth compound having a structure shown in formula 5:
preferably, the mass percentage of the first compound in the nonaqueous electrolyte solution of the lithium ion battery is 0.02% to 5%, for example, may be 0.02%,0.1%,0.5%,1%,2% or 5%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the mass percentage of the cyclic ester additive in the nonaqueous electrolyte of the lithium ion battery is 0.05% to 20%, for example, may be 0.05%,0.5%,1%,5%,10% or 20%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the cyclic ester additive in the nonaqueous electrolyte of the lithium ion battery includes any one or a combination of at least two of a cyclic carbonate additive, a cyclic sulfonate additive, or a cyclic sulfate additive, and for example, the cyclic carbonate additive, the cyclic sulfonate additive, and the cyclic sulfonate additive may be any one of a cyclic carbonate additive, a cyclic sulfonate additive, a cyclic carbonate additive, a cyclic sulfate additive, a cyclic sulfonate additive, and a cyclic sulfate, but not limited to the listed types, and other types not listed in the scope of the cyclic ester additive are equally applicable.
Preferably, the cyclic carbonate additive comprises any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate or ethylene carbonate, for example, vinylene carbonate, fluoroethylene carbonate and ethylene carbonate or ethylene carbonate, but not limited to the listed types, other non-listed types within the scope of the cyclic carbonate additive are equally applicable.
Preferably, the cyclic sultone additive includes any one or a combination of two of 1, 3-propane sultone or 1, 3-propene sultone, and may be, for example, 1, 3-propane sultone and 1, 3-propene sultone, 1, 3-propane sultone or 1, 3-propene sultone.
Preferably, the cyclic sulfate additive includes any one or a combination of at least two of vinyl sulfate or propylene sulfate, and for example, can be vinyl sulfate and propylene sulfate, vinyl sulfate or propylene sulfate.
Preferably, the electrolyte is a lithium salt.
Preferably, the lithium salt comprises lithium hexafluorophosphate.
The concentration of lithium hexafluorophosphate in the nonaqueous electrolyte of the lithium ion battery is preferably 0.5mol/L to 2mol/L, for example, may be 0.5mol/L,1mol/L,1.5mol/L or 2mol/L, but is not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the additive further comprises a lithium salt additive.
Preferably, the lithium salt additive comprises any one or a combination of at least two of lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonimide or lithium bistrifluoromethylsulfonylimide, for example, lithium difluorophosphate and lithium difluorophosphate, lithium difluorooxalato borate or lithium difluorosulfonimide, but not limited to the listed types, and other non-listed types are equally applicable within the scope of the lithium salt additive.
Preferably, the mass percentage of the lithium salt additive in the nonaqueous electrolyte of the lithium ion battery is 0.05% to 20%, for example, 0.05%,0.5%,1%,5%,10% or 20%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the nonaqueous solvent includes any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, propylene carbonate or diethyl carbonate, for example, ethylene carbonate and dimethyl carbonate, ethylmethyl carbonate and propylene carbonate or diethyl carbonate, but not limited to the listed types, and other non-listed types are equally applicable in the nonaqueous solvent range.
Preferably, the mass percentage of the nonaqueous solvent in the nonaqueous electrolyte of the lithium ion battery is 60% to 85%, for example, 60%,65%,70%,75%,80% or 85%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
In a second aspect, the present invention provides a lithium ion battery comprising the lithium ion battery nonaqueous electrolyte of the first aspect.
Preferably, the lithium ion battery further includes a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector, a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector, and a separator.
Preferably, the positive electrode active material includes any one or a combination of at least two of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, and for example, may be lithium cobalt oxide and lithium nickel oxide, lithium manganese oxide and lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide, but not limited to the listed types, and other non-listed types are equally applicable within the scope of the positive electrode active material.
Preferably, the negative electrode active material includes any one or a combination of at least two of soft carbon, hard carbon, artificial graphite, natural graphite, silicon oxy-carbon compound, silicon carbon compound, or lithium titanate, and for example, soft carbon and hard carbon, artificial graphite and natural graphite, silicon oxy-carbon compound, silicon carbon compound, or lithium titanate may be used, but not limited to the listed types, and other non-listed types within the scope of the negative electrode active material are equally applicable.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a non-aqueous electrolyte of a lithium ion battery, which adopts a first compound with a polyalkenyl structure, not only enhances the electron donating effect, but also forms a channel for lithium ion transmission by using the obtained polymer network, and the size of the channel is adjusted by using the number of nodes to promote the transmission of lithium ions, and meanwhile, the stable SEI film is prepared by being used together with a cyclic ester additive, so that the high-temperature cycle performance of the battery is optimized.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The prior art scheme improves the energy density of the lithium ion battery by adopting a positive electrode material with high content of nickel element and improving the charge cut-off voltage. However, the solutions disclosed in the prior art all have adverse effects on the electrolyte, for example, resulting in side reactions, gas production, and increased interfacial resistance.
In order to solve the technical problems, the invention provides a non-aqueous electrolyte of a lithium ion battery and application thereof.
The embodiment part of the invention provides a lithium ion battery nonaqueous electrolyte, which comprises an electrolyte, a nonaqueous solvent and an additive, wherein the additive comprises a first compound with a structure shown in a formula 1 and a cyclic ester additive:
wherein R is 1 、R 2 、R 3 And R is 4 Each independently selected from-ch=ch-X, C2 to C6 linear alkyl or C2 to C6 branched alkyl;
the X is selected from a linear alkyl group of-H, C to C6 or a branched alkyl group of C2 to C6;
the R is 1 、R 2 、R 3 And R is 4 At least one of which is selected from-ch=ch-X.
The invention provides a non-aqueous electrolyte of a lithium ion battery, which adopts a first compound with a polyalkenyl structure, an obtained polymer network forms a channel for lithium ion transmission, the size of the channel is adjusted by utilizing the number of nodes, the transmission of lithium ions is promoted, and meanwhile, the polymer network is used cooperatively with a cyclic ester additive to prepare a stable SEI film, so that the high-temperature cycle performance of the battery is optimized.
In some embodiments, the first compound includes a second compound having a structure represented by formula 2, a third compound having a structure represented by formula 3, a fourth compound having a structure represented by formula 4, and/or a fifth compound having a structure represented by formula 5:
in some embodiments, the mass percentage of the first compound in the lithium ion battery nonaqueous electrolyte is 0.02% to 5%.
In some embodiments, the cyclic ester additive is present in the lithium ion battery nonaqueous electrolyte in an amount of 0.05% to 20% by mass.
In some embodiments, the cyclic ester additive in the lithium ion battery nonaqueous electrolyte comprises any one or a combination of at least two of a cyclic carbonate additive, a cyclic sulfonate additive, or a cyclic sulfate additive.
In some embodiments, the cyclic carbonate additive includes any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate, or ethylene carbonate.
In some embodiments, the cyclic sultone-based additive comprises either 1, 3-propane sultone or 1, 3-propenoic sultone, or a combination of both.
In some embodiments, the cyclic sulfate additive includes any one or a combination of at least two of vinyl sulfate or propylene sulfate.
In some embodiments, the electrolyte is a lithium salt.
In some embodiments, the lithium salt comprises lithium hexafluorophosphate.
In some embodiments, the concentration of lithium hexafluorophosphate in the lithium ion battery non-aqueous electrolyte is 0.5mol/L to 2mol/L.
In some embodiments, the additive further comprises a lithium salt additive.
In some embodiments, the lithium salt additive comprises any one or a combination of at least two of lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorosulfonimide, or lithium bistrifluoromethylsulfonimide.
In some embodiments, the lithium salt additive is present in the lithium ion battery nonaqueous electrolyte in an amount of 0.05% to 20% by mass.
In some embodiments, the nonaqueous solvent comprises any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate, propylene carbonate, or diethyl carbonate.
In some embodiments, the non-aqueous solvent in the non-aqueous electrolyte of the lithium ion battery is 60% to 85% by mass.
In one embodiment, a lithium ion battery comprising the lithium ion battery nonaqueous electrolyte is provided.
In one embodiment, the lithium ion battery further includes a positive electrode current collector and a positive electrode active material coated on the positive electrode current collector, a negative electrode current collector and a negative electrode active material coated on the negative electrode current collector, and a separator.
In an embodiment, the positive electrode active material includes any one or a combination of at least two of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide.
In an embodiment, the negative electrode active material includes any one or a combination of at least two of soft carbon, hard carbon, artificial graphite, natural graphite, silicon, a silicon oxygen compound, a silicon carbon compound, or lithium titanate.
Example 1
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, a fourth compound, 2.5% of vinylene carbonate, 2.5% of 1, 3-propane sultone and 5% of an additive of vinyl sulfate, wherein the lithium salt comprises lithium hexafluorophosphate with a concentration of 1mol/L, lithium difluorophosphate with a concentration of 2.5% respectively, lithium difluorosulfimide with a concentration of 2.5% and lithium difluorophosphate with bisoxalic acid with a concentration of 5%, and the balance of a nonaqueous solvent, and the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, ethylene carbonate, 1, 3-propane sultone and ethylene sulfate in a mass percentage of 2.5% and 2.5% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in a mass percentage of 2.5% and 2.5% respectively, so that the concentration of the lithium hexafluorophosphate is 1mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps:
the positive electrode active material LiNi 0.8 Co 0.1 Mn 0.1 O 2 Fully stirring and uniformly mixing the conductive agent acetylene black and the binder polyvinylidene fluoride in an N-methyl pyrrolidone solvent system according to the mass ratio of 95:3:2, coating the mixture on an aluminum foil, drying and cold pressing the aluminum foil to obtain a positive electrode plate, wherein the compacted density of the positive electrode plate is 3.5g/cm 3 。
The preparation method comprises the steps of fully stirring and uniformly mixing negative electrode active material graphite, conductive agent acetylene black, binder styrene-butadiene rubber and thickener sodium carbomethylcellulose in a deionized water solvent system according to a mass ratio of 96:2:1:1, coating the mixture on a copper foil, drying and cold pressing the mixture to obtain a negative electrode plate, wherein the compaction density of the negative electrode plate is 1.65g/cm 3 。
The separator was obtained by using polyethylene having a thickness of 9 μm as a base film and coating a nano alumina coating having a thickness of 3 μm on the base film.
And sequentially stacking the positive pole piece, the diaphragm and the negative pole piece, so that the diaphragm is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and stacking to obtain the bare cell.
And (3) filling the bare cell into an aluminum plastic film, baking at 80 ℃ to remove water, injecting corresponding electrolyte, sealing, standing, hot-cold pressing, forming, clamping, capacity-dividing and the like to obtain the finished product of the flexible package lithium ion secondary battery.
Example 2
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, a fourth compound, ethylene carbonate and an additive of 1, 3-propane sultone, wherein the mass percentage of the fourth compound, the ethylene carbonate and the additive of 1, 3-propane sultone are respectively 0.02%, the lithium salt comprises lithium hexafluorophosphate with the concentration of 0.5mol/L, lithium difluorophosphate with the mass percentage of 5%, lithium difluorosulfimide and lithium difluorophosphate with the mass percentage of 10%, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of ethylene carbonate, methyl ethyl carbonate and diethyl carbonate according to the mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding the fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, ethylene carbonate and 1, 3-propane sultone in mass percent of 0.02% and 0.025% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percent of 5% and lithium difluorooxalate in mass percent of 10% respectively to ensure that the concentration of the lithium hexafluorophosphate is 0.5mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 3
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, a fourth compound, ethylene carbonate, 1, 3-propane sultone and ethylene sulfate additives, wherein the fourth compound, the ethylene carbonate, the 1, 3-propane sultone and the ethylene sulfate additives are 5% in percentage by mass, the lithium salt comprises lithium hexafluorophosphate with the concentration of 2mol/L, lithium difluorophosphate and lithium difluorosulfimide with the mass percentage of 0.025% and the balance of nonaqueous solvent, and the nonaqueous solvent comprises ethylene carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 based on 100% of the total mass of the nonaqueous electrolyte, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, ethylene carbonate, 1, 3-propane sultone and ethylene sulfate in a mass percentage of 5% respectively, and adding lithium difluorophosphate and lithium difluorosulfimide in a mass percentage of 0.025% respectively so that the concentration of the lithium hexafluorophosphate is 2mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 4
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, a fifth compound, 2.5% of vinylene carbonate, 2.5% of 1, 3-propane sultone and 5% of an additive of vinyl sulfate, wherein the lithium salt comprises lithium hexafluorophosphate with a concentration of 1mol/L, lithium difluorophosphate with a mass percentage of 2.5% respectively, lithium difluorosulfimide with a mass percentage of 2.5% and lithium difluorophosphate with a mass percentage of 5%, and the balance of a nonaqueous solvent, and the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2. .
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fifth compound, ethylene carbonate, 1, 3-propane sultone and ethylene sulfate in a mass percentage of 2.5% and 2.5% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in a mass percentage of 2.5% and 2.5% respectively, so that the concentration of the lithium hexafluorophosphate is 1mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 5
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 0.02% of a fifth compound, 0.025% of vinylene carbonate and 0.025% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 0.5mol/L of lithium hexafluorophosphate, 5% of lithium difluorosulfimide and 10% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent comprises 3:5:2 of ethylene carbonate, ethyl methyl carbonate and diethyl carbonate.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (3) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fifth compound, ethylene carbonate and 1, 3-propane sultone in mass percent of 0.02% and 0.025% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percent of 5% and lithium difluorooxalate in mass percent of 10% respectively to ensure that the concentration of lithium hexafluorophosphate is 0.5mol/L, so as to prepare the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 6
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, a fifth compound, 5% of vinylene carbonate, 10% of 1, 3-propane sultone and 5% of an additive of vinyl sulfate, wherein the lithium salt comprises lithium hexafluorophosphate with a concentration of 2mol/L, lithium difluorophosphate with a mass percentage of 0.025% and lithium difluorosulfimide with a mass percentage of 0.025%, and the balance of a nonaqueous solvent, and the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the ethylmethyl carbonate and the diethyl carbonate battery grade organic solvent in a mass ratio of 3:5:2 based on 100% of the total mass of the nonaqueous electrolyte, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fifth compound, ethylene carbonate, 1, 3-propane sultone and ethylene sulfate in a mass percentage of 5% respectively, and adding lithium difluorophosphate and lithium difluorosulfimide in a mass percentage of 0.025% respectively so that the concentration of lithium hexafluorophosphate is 2mol/L, thereby preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 7
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 0.4% of a fourth compound, 0.1% of a fifth compound, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, and the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate according to a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, a fifth compound, vinyl sulfate, vinylene carbonate and 1% of 1, 3-propane sultone in mass percentages of 0.4% and 0.5% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percentages of 0.8% and 0.5% respectively, so that the concentration of lithium hexafluorophosphate is 1mol/L, and preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 8
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 0.26% of a fourth compound, 0.13% of a fifth compound, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, a fifth compound, vinyl sulfate, vinylene carbonate and 1% of 1, 3-propane sultone in mass percentages of 0.26% and 0.5% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percentages of 0.8% and 0.5% respectively, so that the concentration of lithium hexafluorophosphate is 1mol/L, and preparing the nonaqueous electrolyte of the lithium ion battery.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 9
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 0.16% of a fourth compound, 0.16% of a fifth compound, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, a fifth compound, vinyl sulfate, vinylene carbonate and 1% of 1, 3-propane sultone in mass percentages of 0.16% and 0.5% respectively, and preparing the nonaqueous electrolyte of the lithium ion battery by adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percentages of 0.8% and lithium difluorooxalate in mass percentages of 0.5% respectively, so that the concentration of lithium hexafluorophosphate is 1 mol/L.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 10
The embodiment provides a lithium ion battery nonaqueous electrolyte, which comprises, based on 100% of the total mass of the nonaqueous electrolyte, 0.09% of a fourth compound, 0.18% of a fifth compound, 1% of vinyl sulfate, 0.5% of vinylene carbonate and 1% of an additive of 1, 3-propane sultone, wherein the lithium salt comprises 1mol/L lithium hexafluorophosphate, 0.8% of lithium difluorophosphate, 0.5% of lithium difluorosulfimide and 0.5% of lithium difluorophosphate, and the balance of a nonaqueous solvent, wherein the nonaqueous solvent consists of vinyl carbonate, methyl ethyl carbonate and diethyl carbonate in a mass ratio of 3:5:2.
The preparation method of the nonaqueous electrolyte of the lithium ion battery comprises the following steps: the electrolyte was formulated in a glove box where the nitrogen content was 99.999%, the actual oxygen content in the glove box was 0.1ppm, and the moisture content was 0.1ppm. And (2) uniformly mixing the ethylene carbonate, the methyl ethyl carbonate and the diethyl carbonate battery-grade organic solvent in a mass ratio of 3:5:2 by taking the total mass of the nonaqueous electrolyte as 100%, adding fully dried lithium hexafluorophosphate into the nonaqueous solvent, adding a fourth compound, a fifth compound, vinyl sulfate, vinylene carbonate and 1% of 1, 3-propane sultone in mass percentages of 0.09% and 0.5% respectively, and adding lithium difluorophosphate, lithium difluorosulfimide and lithium difluorophosphate in mass percentages of 0.5% respectively to prepare the nonaqueous electrolyte of the lithium ion battery, wherein the concentration of the lithium hexafluorophosphate is 1 mol/L.
The preparation method of the lithium ion battery comprises the following steps: the preparation method of the lithium ion battery of this example is the same as that of example 1.
Example 11
This example differs from example 1 in that the fourth compound is replaced by a tetravinylsilane, all other things being equal to example 1.
Example 12
This example differs from example 1 in that the fourth compound is replaced with a third compound, all other things being equal to example 1.
Example 13
This example differs from example 1 in that the fourth compound is replaced by diethyldivinylbenzene, all other things being equal to example 1.
Example 14
This example differs from example 1 in that the fourth compound is replaced with the second compound, all other things being equal to example 1.
Comparative example 1
The comparative example differs from example 1 in that the mass percentage of the fourth compound is 20% based on 100% of the total mass of the nonaqueous electrolytic solution, and the total amount of the electrolytic solution is 100% by adaptively adjusting the amount of the nonaqueous solvent, and the other raw materials, the proportions and the mass percentages of the respective components are the same as in example 1.
Comparative example 2
The comparative example differs from example 4 in that the mass percentage of the fifth compound is 20% based on 100% of the total mass of the nonaqueous electrolytic solution, and the total amount of the electrolytic solution is 100% by adaptively adjusting the amount of the nonaqueous solvent, and the other raw materials, the proportions and the mass percentages of the respective components are the same as in example 4.
Comparative example 3
The comparative example differs from example 7 in that the fourth compound and the fifth compound additives are not added, and the amount of the nonaqueous solvent is adaptively adjusted so that the total amount of the electrolyte is 100%, and the other raw materials, the proportions and the mass percentages of the respective components are the same as example 7.
Comparative example 4
The comparative example differs from example 7 in that the mass percentage of the fourth compound is 20% and the mass percentage of the fifth compound is 20% based on 100% of the total mass of the nonaqueous electrolytic solution, and the total amount of the electrolytic solution is 100% by adaptively adjusting the amount of the nonaqueous solvent, and the mass percentages of other raw materials, the mixture ratio and the components are the same as in example 7.
Comparative example 5
The comparative example differs from example 7 in that the fourth compound and the fifth compound additive were not added, tetraethylsilane was added in an amount of 0.5% by mass based on 100% by mass of the total nonaqueous electrolytic solution, and the total amount of the electrolytic solution was adjusted to 100% by mass based on the total amount of the nonaqueous solvent, and the other raw materials, the proportions, and the mass percentages of the respective components were the same as in example 7.
Comparative example 6
The comparative example differs from example 7 in that the fourth compound and the fifth compound additive are not added, tetraethylsilane is added in an amount of 10% by mass based on 100% by mass of the total nonaqueous electrolytic solution, and the total amount of the electrolytic solution is adjusted to 100% by mass of the other raw materials, the proportions and the mass percentages of the respective components are the same as in example 7.
Test conditions
The lithium ion batteries prepared in examples 1 to 14 and comparative examples 1 to 6 were respectively subjected to high-temperature storage performance test by the following test methods:
at 25 ℃, lithium ions are addedThe battery was charged to 4.2V at a constant current of 1C, then charged to a current of less than 0.05C at a constant voltage of 4.2V, then discharged to 3.0V at a constant current of 0.5C, and the discharge capacity of the lithium ion battery at this time was tested and recorded as D 0 The method comprises the steps of carrying out a first treatment on the surface of the Charging to 4.2V with 1C constant current, charging to current less than 0.05C with 4.2V constant voltage, storing the lithium ion battery at 60deg.C for 30 days, and discharging to 3.0V with 1C constant current after storage; then charging to 4.2V with 1C constant current, then charging to current less than 0.05C with 4.2V constant voltage, then discharging to 3.0V with 0.5C constant current, testing discharge capacity of lithium ion battery at this time and marking as D 1 . The capacity retention rate with respect to the lithium ion battery before storage was calculated according to the following formula:
capacity retention (%) = (D) 1 /D 0 )×100％。
The lithium ion battery was charged to 4.2V at a constant current of 1C at 25C, then charged at a constant voltage to a current of 0.05C, and the thickness of the lithium ion battery before storage was measured and recorded as h 0 . Then the battery in full charge state is put into a baking oven at 60 ℃ for 30 days, and the thickness after the storage is tested and recorded as h 1 The thickness expansion ratio with respect to the lithium ion battery before storage was calculated according to the following formula:
thickness expansion ratio (%) = (h) 1 -h 0 )/h 0 ×100％。
The results of the test are shown in table 1:
table 1:
as can be seen from the data in tables 1 and 2, the present invention adopts the nonaqueous electrolyte containing the additive, and by testing the high-temperature storage performance of the lithium ion batteries prepared in the above examples, the capacity retention rate of the lithium ion batteries provided in examples 1 to 14 is more than 86% compared with comparative examples 1 to 4, and in particular, the capacity retention rate of the lithium ion batteries provided in example 10 is more than 98.9%, which further illustrates the advantages of high capacity retention rate and high-temperature stability of the lithium ion batteries prepared by adopting the electrolyte of the present invention; compared with examples 7-10, the electrolyte provided by the invention can relieve the volume expansion of a battery when the additive content is proper and the node number reaches between 2 and 2.5, and therefore, the electrolyte provided by the invention is applied to a lithium ion battery and has excellent high-temperature long-cycle stability, high-temperature storage stability and good safety performance.
Comparative examples 1 and 2 demonstrate that excessive levels of olefinic additives can cause increased resistance, which can prevent improvement in battery performance; comparative example 3 was not added with additives, so that the battery performance was the worst; comparative example 4, in which the fourth compound and the fifth compound are added in excess at the same time, also has a negative effect on the performance of the battery as in comparative examples 1 and 2; comparative examples 5 and 6, to which a tetraethylsilane additive was added, exhibited poor effects in both capacity retention and thickness expansion rate of the battery under high temperature storage conditions, since a stable SEI film could not be formed on the electrode surface by means of oxidative polymerization.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (18)
1. A lithium ion battery nonaqueous electrolyte, comprising an electrolyte, a nonaqueous solvent, and an additive comprising a first compound and a cyclic ester additive:
the first compound includes a fourth compound having a structure shown in formula 4 and a fifth compound having a structure shown in formula 5:
in the lithium ion nonaqueous electrolyte, the mass percentage of the fourth compound is 0.16%, and the mass percentage of the fifth compound is 0.16%;
alternatively, in the lithium ion nonaqueous electrolyte solution, the mass percentage of the fourth compound is 0.09%, and the mass percentage of the fifth compound is 0.18%.
2. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the cyclic ester additive is contained in the lithium ion battery nonaqueous electrolyte in an amount of 0.05 to 20% by mass.
3. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the cyclic ester additive in the lithium ion battery nonaqueous electrolyte comprises any one or a combination of at least two of a cyclic carbonate additive, a cyclic sulfonate additive, or a cyclic sulfate additive.
4. The lithium ion battery nonaqueous electrolyte according to claim 3, wherein the cyclic carbonate-based additive comprises any one or a combination of at least two of vinylene carbonate, fluoroethylene carbonate, and ethylene carbonate.
5. The nonaqueous electrolyte for lithium ion batteries according to claim 3, wherein the cyclic sultone-based additive comprises any one or a combination of two of 1, 3-propane sultone or 1, 3-propenoic sultone.
6. The lithium ion battery nonaqueous electrolyte according to claim 3, wherein the cyclic sulfate-based additive comprises any one or a combination of at least two of vinyl sulfate or propylene sulfate.
7. The lithium ion battery nonaqueous electrolyte of claim 1, wherein the electrolyte is a lithium salt.
8. The lithium ion battery nonaqueous electrolyte of claim 7, wherein the lithium salt comprises lithium hexafluorophosphate.
9. The lithium ion battery nonaqueous electrolyte according to claim 8, wherein a concentration of lithium hexafluorophosphate in the lithium ion battery nonaqueous electrolyte is 0.5mol/L to 2mol/L.
10. The lithium ion battery nonaqueous electrolyte of claim 1, wherein the additive further comprises a lithium salt additive.
11. The lithium ion battery nonaqueous electrolyte of claim 10, wherein the lithium salt additive comprises any one or a combination of at least two of lithium difluorophosphate, lithium difluorooxalato borate, lithium difluorosulfimide, or lithium bistrifluoromethylsulfonimide.
12. The lithium ion battery nonaqueous electrolyte according to claim 10, wherein the mass percentage of the lithium salt additive in the lithium ion battery nonaqueous electrolyte is 0.05% to 20%.
13. The lithium ion battery nonaqueous electrolyte according to claim 1, wherein the nonaqueous solvent comprises any one or a combination of at least two of ethylene carbonate, dimethyl carbonate, methylethyl carbonate, propylene carbonate, and diethyl carbonate.
14. The nonaqueous electrolyte for lithium ion batteries according to claim 1, wherein the nonaqueous solvent in the nonaqueous electrolyte for lithium ion batteries is 60% to 85% by mass.
15. A lithium ion battery characterized in that it comprises the lithium ion battery nonaqueous electrolyte according to any one of claims 1 to 14.
16. The lithium ion battery of claim 15, further comprising a positive current collector and a positive active material coated on the positive current collector, a negative current collector and a negative active material coated on the negative current collector, and a separator.
17. The lithium ion battery of claim 16, wherein the positive electrode active material comprises any one or a combination of at least two of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, or lithium nickel cobalt aluminum oxide.
18. The lithium ion battery of claim 16, wherein the negative electrode active material comprises any one or a combination of at least two of soft carbon, hard carbon, artificial graphite, natural graphite, silicon, a silicon oxygen compound, a silicon carbon compound, or lithium titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111249776.3A CN113809401B (en) | 2021-10-26 | 2021-10-26 | Nonaqueous electrolyte for lithium ion battery and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111249776.3A CN113809401B (en) | 2021-10-26 | 2021-10-26 | Nonaqueous electrolyte for lithium ion battery and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113809401A CN113809401A (en) | 2021-12-17 |
| CN113809401B true CN113809401B (en) | 2024-01-30 |
Family
ID=78937977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111249776.3A Active CN113809401B (en) | 2021-10-26 | 2021-10-26 | Nonaqueous electrolyte for lithium ion battery and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113809401B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20240021293A (en) * | 2022-05-09 | 2024-02-16 | 컨템포러리 엠퍼렉스 테크놀로지 씨오., 리미티드 | Electrolyte, secondary batteries, battery modules, battery packs and electrical devices |
| CN116344916B (en) * | 2023-05-29 | 2023-09-08 | 宁德时代新能源科技股份有限公司 | Lithium secondary battery and electricity utilization device |
| CN118099529A (en) * | 2024-04-28 | 2024-05-28 | 广州天赐高新材料股份有限公司 | Electrolyte additive, electrolyte and battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101217204A (en) * | 2007-01-04 | 2008-07-09 | 株式会社东芝 | Nonaqueous electrolyte battery, battery pack and vehicle |
| CN101283466A (en) * | 2005-10-10 | 2008-10-08 | 苏威氟有限公司 | Fluorinated additives for lithium ion batteries |
| JP2010092748A (en) * | 2008-10-09 | 2010-04-22 | Denso Corp | Nonaqueous electrolyte for secondary battery and nonaqueous electrolyte secondary battery using this electrolyte solution |
| WO2012111335A1 (en) * | 2011-02-18 | 2012-08-23 | 三洋化成工業株式会社 | Agent for forming electrode protection film |
| KR20170038540A (en) * | 2015-09-30 | 2017-04-07 | 주식회사 엘지화학 | Lithium secondary battery comprising non-aqueous liquid electrolyte |
| CN109921092A (en) * | 2019-03-06 | 2019-06-21 | 杉杉新材料（衢州）有限公司 | A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte |
| CN112531212A (en) * | 2020-12-09 | 2021-03-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte with high-temperature characteristic and low impedance, application thereof and lithium ion battery |
| CN113161613A (en) * | 2021-04-19 | 2021-07-23 | 杉杉新材料（衢州）有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113394451A (en) * | 2021-07-09 | 2021-09-14 | 杉杉新材料（衢州）有限公司 | Lithium ion battery electrolyte containing unsaturated bond silane additive and lithium ion battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9123971B2 (en) * | 2010-09-02 | 2015-09-01 | Nec Corporation | Secondary battery |
-
2021
- 2021-10-26 CN CN202111249776.3A patent/CN113809401B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101283466A (en) * | 2005-10-10 | 2008-10-08 | 苏威氟有限公司 | Fluorinated additives for lithium ion batteries |
| CN101217204A (en) * | 2007-01-04 | 2008-07-09 | 株式会社东芝 | Nonaqueous electrolyte battery, battery pack and vehicle |
| JP2010092748A (en) * | 2008-10-09 | 2010-04-22 | Denso Corp | Nonaqueous electrolyte for secondary battery and nonaqueous electrolyte secondary battery using this electrolyte solution |
| WO2012111335A1 (en) * | 2011-02-18 | 2012-08-23 | 三洋化成工業株式会社 | Agent for forming electrode protection film |
| KR20170038540A (en) * | 2015-09-30 | 2017-04-07 | 주식회사 엘지화학 | Lithium secondary battery comprising non-aqueous liquid electrolyte |
| CN109921092A (en) * | 2019-03-06 | 2019-06-21 | 杉杉新材料（衢州）有限公司 | A kind of silicon-based anode non-aqueous electrolyte for lithium ion cell and the silicon-based anode lithium ion battery containing the electrolyte |
| CN112531212A (en) * | 2020-12-09 | 2021-03-19 | 远景动力技术(江苏)有限公司 | Non-aqueous electrolyte with high-temperature characteristic and low impedance, application thereof and lithium ion battery |
| CN113161613A (en) * | 2021-04-19 | 2021-07-23 | 杉杉新材料（衢州）有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113394451A (en) * | 2021-07-09 | 2021-09-14 | 杉杉新材料（衢州）有限公司 | Lithium ion battery electrolyte containing unsaturated bond silane additive and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| Formation of unexpected silicon-and disiloxane-bridged multiferrocenyl derivatives bearing Si-O-CH=CH2 and Si-(CH2)2C(CH3)3 substituents via cleavage of tetrahydrofuran and trapping of its ring fragments;Sonia Bruña等;DALTON TRANSACTIONS;第46卷(第35期);11584-11597 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113809401A (en) | 2021-12-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111628218B (en) | Lithium ion battery and preparation method thereof | |
| CN113809401B (en) | Nonaqueous electrolyte for lithium ion battery and application thereof | |
| CN108232296B (en) | Electrolyte solution and lithium secondary battery | |
| CN113991178B (en) | Nonaqueous electrolyte for lithium ion battery and application thereof | |
| CN113078354A (en) | Ternary lithium ion battery non-aqueous electrolyte and lithium ion battery thereof | |
| CN112635835B (en) | High-low temperature compatible non-aqueous electrolyte and lithium ion battery | |
| CN112467209A (en) | High-voltage lithium ion battery with high and low temperature performance | |
| CN109687026B (en) | High-voltage ternary lithium ion battery electrolyte and lithium ion battery containing same | |
| CN112448033A (en) | High-voltage lithium ion battery electrolyte and long-cycle-life high-voltage lithium ion battery | |
| CN111834665B (en) | High-nickel ternary lithium ion battery electrolyte and lithium ion battery | |
| CN108390098B (en) | High-voltage lithium ion battery electrolyte and high-voltage lithium ion battery | |
| CN114142091A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN110783628A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
| KR20100031019A (en) | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same | |
| CN112290090A (en) | High-nickel ternary lithium ion battery non-aqueous electrolyte and battery containing electrolyte | |
| CN113964385B (en) | Electrolyte, preparation method and application thereof | |
| CN106941191B (en) | Lithium ion battery and non-aqueous electrolyte thereof | |
| CN115117443A (en) | Electrolyte suitable for lithium metal negative electrode secondary battery | |
| CN114709480B (en) | Nonaqueous electrolyte and lithium ion battery thereof | |
| CN112310475A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN114899484B (en) | Nonaqueous electrolyte and lithium ion battery thereof | |
| CN114709481B (en) | Nonaqueous electrolyte and lithium ion battery thereof | |
| CN114709479B (en) | Nonaqueous electrolyte and lithium ion battery thereof | |
| CN113948770B (en) | Electrolyte for improving high-temperature storage characteristics of battery and lithium ion battery | |
| CN114335731A (en) | Non-aqueous electrolyte and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |