CN114497736B - Electrolyte and battery containing same - Google Patents
Electrolyte and battery containing same Download PDFInfo
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- CN114497736B CN114497736B CN202210039430.9A CN202210039430A CN114497736B CN 114497736 B CN114497736 B CN 114497736B CN 202210039430 A CN202210039430 A CN 202210039430A CN 114497736 B CN114497736 B CN 114497736B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 120
- 239000000654 additive Substances 0.000 claims abstract description 110
- 230000000996 additive effect Effects 0.000 claims abstract description 110
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 44
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 12
- 125000004122 cyclic group Chemical group 0.000 claims description 9
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 6
- 125000003601 C2-C6 alkynyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 24
- -1 sulfonamide compounds Chemical class 0.000 abstract description 16
- 239000007772 electrode material Substances 0.000 abstract description 8
- 230000035939 shock Effects 0.000 abstract description 8
- 229940124530 sulfonamide Drugs 0.000 abstract description 7
- 239000007773 negative electrode material Substances 0.000 abstract description 6
- 238000004090 dissolution Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 abstract description 5
- 238000006722 reduction reaction Methods 0.000 abstract description 4
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 150000005676 cyclic carbonates Chemical group 0.000 description 18
- 229940125898 compound 5 Drugs 0.000 description 17
- 150000005678 chain carbonates Chemical class 0.000 description 16
- 229910052759 nickel Inorganic materials 0.000 description 15
- 229910003002 lithium salt Inorganic materials 0.000 description 14
- 159000000002 lithium salts Chemical class 0.000 description 14
- 239000007774 positive electrode material Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000007600 charging Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 229910013870 LiPF 6 Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000002153 silicon-carbon composite material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004969 haloethyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004970 halomethyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an electrolyte and a battery containing the electrolyte, wherein the electrolyte comprises electrolyte salt, an organic solvent and an additive, and the additive comprises a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from sulfonate compounds. According to the invention, through the synergistic effect of the first additive and the second additive, the film can be formed on the surface of the positive electrode, the direct contact of the electrode material and the electrolyte is avoided, the microstructure of the electrode material is stabilized, the dissolution of transition metal elements at high temperature is reduced, the SEI film can be formed on the surface of the negative electrode material, the reduction reaction of the solvent at the interface of the negative electrode is inhibited, and the high-temperature storage performance, the high-temperature cycle performance, the low-temperature discharge performance and the thermal shock performance of the battery can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of batteries, and relates to an electrolyte and a battery containing the same.
Background
In many application fields, a higher requirement is put on the cruising ability of a battery, and in order to improve the energy density of the battery, development of a positive electrode material for a battery with a high specific capacity is one of effective methods.
The high nickel positive electrode material is a research hot spot due to the fact that the theoretical specific capacity of the high nickel positive electrode material is higher than that of other positive electrode materials. Currently common high nickel positive electrode materials include NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 )，NCA(LiNi 0.8 Co 0.15 Al 0.05 O 2 ) Etc.
However, the high nickel cathode material has high nickel metal content, so that the high nickel cathode material has strong oxidizing property, so that electrolyte is easy to generate electrochemical oxidation reaction on the surface of the cathode, meanwhile, the structure of the high nickel cathode material is changed, and transition metals such as nickel, cobalt and the like are dissolved out by reduction reaction, thereby causing the deterioration of the electrochemical performance of the battery. Therefore, it is critical to develop an electrolyte that matches the high nickel positive electrode material.
Disclosure of Invention
In order to solve the series of problems of battery core performance deterioration and the like caused by the strong oxidizing property of the high-nickel positive electrode material in the prior art, the invention provides an electrolyte and a battery containing the electrolyte, wherein the electrolyte is suitable for the battery assembled by the high-nickel positive electrode material, the battery assembled by the electrolyte has excellent high-temperature cycle performance and high-temperature storage life, the gas production rate in the high-temperature storage process (the thickness expansion rate of the battery after high-temperature storage is low) can be remarkably reduced, and meanwhile, the battery also has good thermal shock performance and low-temperature discharge performance.
The invention aims at realizing the following technical scheme:
an electrolyte comprising an electrolyte salt, an organic solvent, and an additive, the additive comprising a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from sulfonate compounds.
According to an embodiment of the present invention, the first additive may be obtained after commercial purchase or may be prepared using methods known in the art.
According to an embodiment of the present invention, the first additive is selected from at least one of a compound represented by formula I or a compound represented by formula II:
in the formula I and the formula II, R 1 Selected from substituted or unsubstituted aryl groups, if substituted aryl groups, said substituents being selected from alkyl, haloalkyl or halogen;
in the formula I, R 2 And R is 3 The same or different, independently of one another, from alkyl groups;
in formula II, the N-containing ring group is a saturated ring group containing at least one N atom.
According to an embodiment of the invention, in formula I and formula II, R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and the substituents are selected from the group consisting of C 1-6 Alkyl (e.g. C 1-4 Alkyl groups, particularlyMethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), halogenated C 1-6 Alkyl (e.g. halogenated C 1-4 Alkyl, in particular halomethyl, haloethyl, halon-propyl, haloisopropyl, halon-butyl, haloisobutyl or halotert-butyl, in particular trifluoromethyl) or halogen (for example F, cl, br or I, in particular F).
According to an embodiment of the invention, in formula I, R 2 And R is 3 Identical or different, independently of one another, from C 1-6 Alkyl radicals, e.g. C 1-4 Alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl.
According to an embodiment of the invention, in formula II, the N-ring containing group is unsubstituted or optionally substituted with one or more R's containing at least one N atom a Substituted saturated cyclic groups;
R a is halogen, -CN, -NO 2 、-NH 2 、-CO-NH 2 Unsubstituted or optionally substituted by one or more R b Substituted as follows: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl;
R b is halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl groups.
According to an embodiment of the invention, in formula II, the saturated cyclic group is a 4-10 membered saturated cyclic group (e.g. a 5-8 membered saturated cyclic group, in particular a 5-membered saturated cyclic group, a 6-membered saturated cyclic group, a 7-membered saturated cyclic group or an 8-membered saturated cyclic group).
According to an embodiment of the present invention, in formula II, the number of heteroatoms in the N-ring containing group may be one, two or more than three. When two or more heteroatoms are present, one is an N atom, and the other may be at least one of an N atom, an O atom, or an S atom.
According to an embodiment of the present invention, in formula II, the N-ring containing group is selected from one of the N-ring containing groups shown below:
wherein, represent the connection.
According to an embodiment of the present invention, the first additive is selected from at least one of the following compounds 1 to 8:
according to an embodiment of the present invention, the second additive may be obtained commercially or may be prepared by methods known in the art.
According to an embodiment of the present invention, the second additive is selected from at least one of a compound represented by formula III or a compound represented by formula IV:
in the formula IV, m is 0, 1, 2, 3 or 4;
R 4 selected from H, halogen, unsubstituted or optionally substituted by one, two or more R' a Substituted with the following groups: c (C) 1-6 Alkyl, C 2-6 Alkenyl, sulfonate (-SO) 3 H)；
Each R' a The same or different, independently of one another, are selected from halogen, C 1-6 An alkyl group.
According to an embodiment of the invention, in formula IV, R 4 Selected from H, propenyl, halogen or-SO 3 F。
According to an embodiment of the present invention, the second additive is at least one selected from the group consisting of a compound represented by formula III, compound 9 to compound 12:
according to an embodiment of the invention, the first additive comprises 0.1wt% to 1wt% of the total mass of the electrolyte, for example 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt% or any point value in the range consisting of two points.
According to an embodiment of the invention, the mass of the second additive is 0.5wt% to 2wt%, for example 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.2wt%, 1.5wt%, 1.7wt%, 1.8wt%, 2wt% or any point value in the range consisting of two point values.
According to the embodiment of the invention, if the addition amount of the sulfonamide compound in the electrolyte is excessive, the impedance of the battery is larger, and the high-temperature cycle performance and the low-temperature discharge performance are reduced; if the addition amount of the sulfonamide compound in the electrolyte is too small, the acid removal, water removal and film forming effects of the additive are poor, and the thermal shock performance, high-temperature cycle performance and high-temperature storage performance of the battery are obviously reduced.
According to the embodiment of the invention, if the addition amount of the sulfonate compound in the electrolyte is excessive, the impedance of the battery is large, and the high-temperature cycle performance and the low-temperature discharge performance are reduced; if the addition amount of the sulfonate compound in the electrolyte is too small, the film forming effect on the surface of a positive electrode material (particularly a high-nickel positive electrode material) and the surface of a negative electrode material (particularly a silicon-carbon negative electrode material) is poor, and the high-temperature cycle performance and the high-temperature storage performance of the battery are reduced.
According to an embodiment of the present invention, the electrolyte salt includes at least one of an electrolyte lithium salt, an electrolyte sodium salt, an electrolyte magnesium salt, an electrolyte aluminum salt, an electrolyte zinc salt, and the like.
According to an embodiment of the invention, the lithium electrolyte salt is selected from LiPF 6 、LiBF 4 、LiClO 4 、LiAsF 6 、LiSO 2 CF 3 、LiN(CF 3 SO 2 ) 2 LiBOB, liDFOB or LiN (C) 2 F 5 SO 2 ) 2 At least one of them.
According to an embodiment of the invention, the organic solvent is selected from cyclic carbonates and/or chain carbonates.
Preferably, the cyclic carbonate is selected from at least one of ethylene carbonate, propylene carbonate or gamma-butyrolactone.
Preferably, the chain carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, methylpropyl carbonate or ethylpropyl carbonate.
According to an embodiment of the invention, the organic solvent is a cyclic carbonate and a chain carbonate.
Preferably, the mass ratio of cyclic carbonate to chain carbonate is 1 (2-3), e.g. 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8 or 1:3.
According to the embodiment of the invention, the electrolyte has reasonable viscosity and conductivity, and ensures better electrochemical performance. When the content of the cyclic carbonate is too low, the conductivity is low although the viscosity of the electrolyte is low, the polarization of the battery is increased, and the cycle and rate performance are poor; when the cyclic carbonate content is too high, the viscosity of the electrolyte increases, the polarization of the battery is also large, and the electrochemical performance is lowered.
According to an embodiment of the invention, the electrolyte salt is present in an amount of 12.5wt% to 20wt%, for example 12.5wt%, 13wt%, 14wt%, 15wt%, 16wt%, 17wt%, 18wt%, 19wt%, 20wt% or any point in the range consisting of the two values.
The invention also provides a preparation method of the electrolyte, which comprises the following steps:
mixing electrolyte salt, an organic solvent and an additive to prepare the electrolyte;
wherein the additive comprises a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from sulfonate compounds.
The invention also provides a battery, which comprises the electrolyte.
According to an embodiment of the invention, the battery further comprises a positive plate, a negative plate and a diaphragm arranged between the positive plate and the negative plate at intervals.
According to an embodiment of the present invention, the charge cut-off voltage of the battery is greater than or equal to 4.2V.
According to an embodiment of the invention, the battery is a lithium ion battery.
As an improvement of the battery of the present invention, the positive electrode sheet includes a positive electrode current collector and a positive electrode membrane including a positive electrode active material, which is a high nickel positive electrode material.
In the invention, the chemical formula of the high-nickel positive electrode material is LiNi 1-x-y-z Co x Mn y Al z O 2 Wherein: 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, and 0.6 is more than or equal to 1-x-y-z is more than or equal to 1. Illustratively, the high nickel positive electrode material is selected from NCM811 (LiNi 0.8 Co 0.1 Mn 0.1 O 2 )、NCM622(LiNi 0.6 Co 0.2 Mn 0.2 O 2 )、NCMA89(LiNi 0.89 Co 0.05 Mn 0.05 Al 0.01 O 2 )、NCA(LiNi 0.8 Co 0.15 Al 0.05 O 2 ) At least one of them.
As an improvement of the battery of the present invention, the negative electrode sheet includes a negative electrode current collector and a negative electrode film including a negative electrode active material of SiO w Silicon-carbon composite material compounded with graphite 1<w<2。
The invention has the beneficial effects that:
the invention provides an electrolyte and a battery containing the electrolyte, wherein the electrolyte comprises electrolyte salt, an organic solvent and an additive, and the additive comprises a first additive and a second additive; the first additive is selected from sulfonamide compounds, and the second additive is selected from sulfonate compounds.
The lone electron pair on the N atom in the N-containing ring group and the ortho-connected aromatic ring (such as benzene ring) in the first additive in the electrolyte provided by the invention enable the electrolyte to have higher electron cloud density, and a small amount of the electrolyte is added into the electrolyte to show stronger Lewis basicity. In a first aspect, a first additive is capable of reacting with PF in an electrolyte 5 Formation of complex (lithium hexafluorophosphate has poor thermal stability and is liable to undergo decomposition reaction: liPF) 6 →LiF+PF 5 Generated PF 5 The chemical property is active, and the electrolyte can react with proton impurities existing in trace amount in the electrolyte, so that the acidity and chromaticity of the electrolyte are quickly increased, the quality of the electrolyte is further deteriorated, and the high-temperature cycle performance and the high-temperature storage performance of the battery are reduced, so that the acidity and the reactivity of the electrolyte are reduced, and the increase of the free acid of the electrolyte is inhibited; in the second aspect, the first additive is easily oxidized and decomposed on the surface of the positive electrode in the electrolyte to form an interfacial film, so that direct contact between the electrode material and the electrolyte is avoided, the microstructure of the electrode material is stabilized, dissolution of transition metal elements at high temperature is reduced, and the high-temperature cycle performance and the high-temperature storage performance of the battery are improved;
the sulfonate compound is used as a second additive, wherein oxygen-sulfur bonds are unstable and are easy to generate oxidation ring opening, a passivation film is formed on the surface of the positive electrode, the dissolution of metal ions of the positive electrode is inhibited, and meanwhile, the decomposition effect of active substances in a high oxidation state on a solvent is reduced, so that the electrochemical performance of the battery under the high-temperature condition can be improved; in addition, after the sulfonate compound is decomposed, the aromatic ring or the heteroaromatic ring enables the surface of the negative electrode of the battery to form a stable, uniform and light SEI film, and the decomposition of the solvent in the electrolyte can be inhibited.
In addition, the main components of the SEI film formed by the first additive and the second additive are inorganic lithium sulfide, lithium sulfite and organic lithium salt, the SEI film comprises an inner inorganic layer and an outer organic layer, the outer organic layer has a porous structure, ion migration is facilitated, the inner inorganic layer is beneficial to ion export, and thus the low-temperature performance of the battery is obviously improved.
In summary, through the synergistic effect of the first additive and the second additive, the invention can form a film on the surface of the positive electrode, avoid the direct contact of the electrode material and the electrolyte, stabilize the microstructure of the electrode material, reduce the dissolution of transition metal elements at high temperature, form an SEI film on the surface of the negative electrode material, inhibit the reduction reaction of the solvent at the interface of the negative electrode, and effectively improve the high-temperature storage performance, the high-temperature cycle performance, the low-temperature discharge performance and the thermal shock performance of the battery.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
In the description of the present invention, it should be noted that the terms "first," "second," and the like are used for descriptive purposes only and are not indicative or implying relative importance.
Example 1
The present embodiment provides an electrolyte composed of a cyclic carbonate, a chain carbonate, a lithium salt, and an additive.
The additive comprises a first additive and a second additive, wherein the first additive is selected from a compound 1, the second additive is selected from a compound shown in a formula III, the cyclic carbonate is ethylene carbonate, the chain carbonate is dimethyl carbonate, and the lithium salt is LiPF 6 。
The mass ratio of the cyclic carbonate to the chain carbonate is 1:2.5; the mass of the lithium salt is 13wt% of the total mass of the electrolyte; the mass of the first additive is 0.3wt% of the total mass of the electrolyte; the mass of the second additive is 1.2wt% of the total mass of the electrolyte.
The invention provides a preparation method of the electrolyte, which comprises the following steps: and stirring and mixing the cyclic carbonate, the chain carbonate, the lithium salt and the additive in the formula amount at 25 ℃ to obtain the electrolyte.
Example 2
The present embodiment provides an electrolyte composed of a cyclic carbonate, a chain carbonate, a lithium salt, and an additive.
The additive comprises a first additive and a second additive, wherein the first additive is selected from a compound 2, the second additive is selected from a compound shown in a formula III, the cyclic carbonate is gamma-butyrolactone, the chain carbonate is ethylmethyl carbonate, and the lithium salt is LiPF 6 。
The mass ratio of the cyclic carbonate to the chain carbonate is 1:2; the mass of the lithium salt is 13wt% of the total mass of the electrolyte; the mass of the first additive is 0.3wt% of the total mass of the electrolyte; the mass of the second additive is 1.2wt% of the total mass of the electrolyte.
The invention provides a preparation method of the electrolyte, which comprises the following steps: and stirring and mixing the cyclic carbonate, the chain carbonate, the lithium salt and the additive in the formula amount at 25 ℃ to obtain the electrolyte.
Example 3
The present embodiment provides an electrolyte composed of a cyclic carbonate, a chain carbonate, a lithium salt, and an additive.
The additive comprises a first additive and a second additive, wherein the first additive is selected from a compound 3, the second additive is selected from a compound shown in a formula III, the cyclic carbonate is propylene carbonate, the chain carbonate is diethyl carbonate, and the lithium salt is LiPF 6 。
The mass ratio of the cyclic carbonate to the chain carbonate is 1:3; the mass of the lithium salt is 13wt% of the total mass of the electrolyte; the mass of the first additive is 0.3wt% of the total mass of the electrolyte; the mass of the second additive is 1.2wt% of the total mass of the electrolyte.
The invention provides a preparation method of the electrolyte, which comprises the following steps: and stirring and mixing the cyclic carbonate, the chain carbonate, the lithium salt and the additive in the formula amount at 25 ℃ to obtain the electrolyte.
Example 4
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 4 and the compound of formula III (the first additive was selected from compound 4 and the second additive was selected from the compound of formula III).
Example 5
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 5 and the compound of formula III (the first additive was selected from compound 5 and the second additive was selected from the compound of formula III).
Example 6
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 6 and the compound of formula III (the first additive was selected from compound 6 and the second additive was selected from the compound of formula III).
Example 7
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 7 and the compound of formula III (the first additive was selected from compound 7 and the second additive was selected from the compound of formula III).
Example 8
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 8 and the compound of formula III (the first additive was selected from compound 8 and the second additive was selected from the compound of formula III).
Example 9
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 5 and compound 9 (the first additive was selected from compound 5 and the second additive was selected from compound 9).
Example 10
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 5 and compound 10 (the first additive was selected from compound 5 and the second additive was selected from compound 10).
Example 11
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 5 and compound 11 (the first additive was selected from compound 5 and the second additive was selected from compound 11).
Example 12
The electrolyte provided in this example was the same as the electrolyte of example 1 except that the additive combination consisted of compound 5 and compound 12 (the first additive was selected from compound 5 and the second additive was selected from compound 12).
Example 13
The electrolyte provided in this example was the same as the electrolyte of example 5 except that the content of compound 5 was 0.05 wt%.
Example 14
The electrolyte provided in this example was the same as the electrolyte of example 5 except that the content of compound 5 was 1.5 wt%.
Example 15
The electrolyte provided in this example was the same as the electrolyte of example 5 except that the compound of formula III was contained in an amount of 0.2 wt%.
Example 16
The electrolyte provided in this example was the same as the electrolyte of example 5 except that the compound of formula III was contained in an amount of 3 wt%.
Comparative example 1
The comparative example was identical to the electrolyte of example 5 except that the additive consisted of only compound 5 and did not contain the compound of formula III.
Comparative example 2
The comparative example was identical to the electrolyte of example 5 except that the additive consisted of only the compound of formula III and did not contain compound 5.
Test method
The electrolyte provided in the above examples or comparative examples was used as the electrolyte of the test cell, and the PP separator was used as the separator of the test cell. The current collector of the positive plate of the test battery is aluminum foil, and the positive coating consists of NCM811, acetylene black and PVDF in a mass ratio of 95:3:2; the current collector of the negative plate of the test battery is copper foil, and the negative electrode coating consists of a silicon-carbon composite material, acetylene black and SBR in a mass ratio of 94:3:3. And assembling the positive pole piece, the negative pole piece, the PP diaphragm and the electrolyte into a 3.0Ah cylindrical battery with the specification of 18650. And (5) performing electrochemical test by adopting a blue-electricity charge-discharge test cabinet.
(1) High temperature cycle performance test
The battery was charged at a constant current of 1C (nominal capacity) to a voltage of 4.2V, then charged at a constant voltage of 4.2V to a current of 0.05C, and after 10min of rest, discharged at a constant current of 1C to a voltage of 2.8V, above which is a charge-discharge cycle. The battery was subjected to 500 charge-discharge cycles at 45℃according to the above conditions.
The capacity retention (%) = (discharge capacity of the nth cycle/first discharge capacity) ×100% after N cycles of the battery, N being the number of cycles of the battery.
(2) High temperature storage test at 60 ℃ for 14 days
Charging and discharging the battery at normal temperature for 1 time (4.20V-2.8V) at 1C, recording the discharge capacity C0 of the battery before storage, then charging the battery to 4.20V full state at constant current and constant voltage, testing the thickness d1 of the battery before high-temperature storage (two diagonal lines of the battery are respectively connected through a straight line, and the intersection point of the two diagonal lines is a battery thickness test point) by using a vernier caliper, placing the battery into a 60 ℃ incubator for storage for 14 days, taking out the battery after storage is completed, testing the thermal thickness d2 of the battery after storage, and calculating the thickness expansion rate of the battery after storage at 60 ℃ for 14 days; after the battery is cooled for 24 hours at room temperature, the battery is discharged to 2.8V at a constant current of 1C, then the battery is charged to 4.20V at a constant current and constant voltage of 1C, the discharge capacity C1 and the charge capacity C2 of the battery after storage are recorded, and the residual capacity retention rate and the recovery capacity retention rate of the battery after storage at 60 ℃ for 14 days are calculated, wherein the calculation formula is as follows:
thickness expansion ratio = (d 2-d 1)/d 1 x 100% after 14 days of storage at 60 ℃;
residual capacity retention = C1/C0 x 100% after 14 days storage at 60 ℃;
recovery capacity retention = C2/C0 x 100% after 14 days storage at 60 ℃.
(3) -10 ℃ rate discharge performance test
At 25 ℃, the battery is discharged to 2.8V at constant current of 0.5C, after being placed for 10min, the battery is charged to 0.05C at constant current of 4.2V at constant voltage of 1C, the battery core is moved to a high-low temperature box of-10 ℃, after being placed for 120min, the battery is discharged to 2.8V at constant current of 4C/7C, and the inflection point voltage is recorded.
(4) Thermal shock property
Discharging to 2.8V at a given current of 0.2C under ambient conditions of 25 ℃; standing for 5min; charging to 4.20V at a charging current of 0.2C, and changing to 4.20V constant voltage charging when the voltage of the battery cell reaches 4.20V until the charging current is less than or equal to a given cutoff current of 0.05C; placing the battery cell into an oven after the battery cell is placed for 1h, raising the temperature of the oven to 130+/-2 ℃ at the speed of 5+/-2 ℃/min, and stopping after the battery cell is kept for 30min, wherein the judgment standard is that the battery cell is not fired and exploded, and the battery cell is marked as pass.
Table 1 comparison of battery test results for examples 1-16 and comparative examples 1-2
From the above examples 1 to 16 and comparative examples 1 to 2, it is apparent that the synergistic effect of the sulfonamide compound and the sulfonate compound in the electrolyte provided in examples 1 to 16 can form a film on the surface of the positive electrode, avoid direct contact between the electrode material and the electrolyte and stabilize the microstructure of the electrode material, reduce dissolution of the transition metal element at high temperature, form an SEI film on the surface of the negative electrode material, inhibit the reduction reaction of the solvent at the interface of the negative electrode, and effectively improve the high-temperature storage performance, high-temperature cycle performance, low-temperature discharge performance and thermal shock performance of the battery.
Example 13 the thermal shock property, the high temperature cycle property and the high temperature storage property of the battery were deteriorated because the amount of the compound 5 added was small. In example 14, the addition amount of the compound 5 was too large, resulting in too high film formation resistance, and the high-temperature cycle and low-temperature discharge performance of the battery were degraded.
Example 15 because the amount of the compound represented by formula III added is small, the protection of the negative electrode is insufficient, the volume of the negative electrode expands with the circulation, the SEI film is continuously destroyed and repaired, the electrolyte is consumed to produce gas, and the high-temperature cycle performance of the battery is reduced and the high-temperature stored gas production is increased. Example 16 the resistance of the battery was large and the low-temperature discharge performance and the high-temperature cycle performance were deteriorated because the amount of the compound represented by formula III added was large.
Comparative example 1 was poor in heat shock performance and high temperature cycle performance of the battery because it did not contain compound 5. Comparative example 2, because it does not contain the compound represented by formula III, results in a significant decrease in the high temperature cycle performance and the high temperature storage performance of the battery.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrolyte comprising an electrolyte salt, an organic solvent and an additive, wherein the additive comprises a first additive and a second additive;
the first additive is selected from at least one of a compound shown in a formula I or a compound shown in a formula II:
in the formula I and the formula II, R 1 Selected from substituted or unsubstituted aryl, if substituted aryl, the substituents are selected from alkyl, haloalkyl or halogen;
in the formula I, R 2 And R is 3 The same or different, independently of one another, from alkyl groups;
in the formula II, the N-containing ring group is a saturated ring group containing at least one N atom;
the second additive is selected from at least one of a compound shown in a formula III or a compound shown in a formula IV:
in the formula IV, m is 0, 1, 2, 3 or 4;
R 4 selected from H, halogen, unsubstituted or optionally substituted by one, two or more R' a Substituted with the following groups: c (C) 1-6 Alkyl, C 2-6 Alkenyl, sulfonate (-SO) 3 H)；
Each R' a The same or different, independently of one another, are selected from halogen, C 1-6 An alkyl group.
2. According to claim 1Is characterized in that in the formula I and the formula II, R 1 Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, and the substituents are selected from the group consisting of C 1-6 Alkyl, halogenated C 1-6 Alkyl or halogen;
and/or, in formula I, R 2 And R is 3 Identical or different, independently of one another, from C 1-6 An alkyl group.
3. The electrolyte of claim 1 wherein in formula II the N-ring containing group is unsubstituted or optionally substituted with one or more R containing at least one N atom a Substituted saturated cyclic groups;
R a is halogen, -CN, -NO 2 、-NH 2 、-CO-NH 2 Unsubstituted or optionally substituted by one or more R b Substituted as follows: c (C) 1-6 Alkyl, C 1-6 Alkoxy, C 2-6 Alkenyl, C 2-6 Alkynyl;
R b is halogen, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 3-6 Cycloalkyl groups.
4. The electrolyte of claim 3 wherein in formula II, the N-ring containing group is selected from one of the N-ring containing groups shown below:
wherein, represent the connection.
5. The electrolyte according to any one of claims 1 to 4, wherein the first additive is selected from at least one of the following compounds 1 to 8:
6. the electrolyte according to any one of claims 1 to 4, wherein the second additive is at least one selected from the group consisting of a compound represented by formula III and compounds 9 to 12:
7. the electrolyte according to any one of claims 1 to 4, wherein the first additive is present in an amount of 0.1 to 1wt% based on the total mass of the electrolyte.
8. The electrolyte according to any one of claims 1 to 4, wherein the mass of the second additive is 0.5 to 2wt% based on the total mass of the electrolyte.
9. The electrolyte of claim 6, wherein the mass of the second additive is 0.5wt% to 2wt% of the total mass of the electrolyte.
10. A battery, characterized in that it comprises the electrolyte according to any one of claims 1-9.
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| JP2004087168A (en) * | 2002-08-23 | 2004-03-18 | Mitsui Chemicals Inc | Nonaqueous electrolytic solution and lithium secondary battery including it |
| JP2016001567A (en) * | 2014-06-12 | 2016-01-07 | 日本電気株式会社 | Electrolyte and secondary battery using the same |
| CN109904521A (en) * | 2017-12-08 | 2019-06-18 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery comprising same |
| CN113839095A (en) * | 2021-10-19 | 2021-12-24 | 珠海冠宇电池股份有限公司 | Electrolyte and battery comprising same |
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| US20050106470A1 (en) * | 2003-01-22 | 2005-05-19 | Yoon Sang Y. | Battery having electrolyte including one or more additives |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004087168A (en) * | 2002-08-23 | 2004-03-18 | Mitsui Chemicals Inc | Nonaqueous electrolytic solution and lithium secondary battery including it |
| JP2016001567A (en) * | 2014-06-12 | 2016-01-07 | 日本電気株式会社 | Electrolyte and secondary battery using the same |
| CN109904521A (en) * | 2017-12-08 | 2019-06-18 | 宁德时代新能源科技股份有限公司 | Electrolyte and battery comprising same |
| CN113839095A (en) * | 2021-10-19 | 2021-12-24 | 珠海冠宇电池股份有限公司 | Electrolyte and battery comprising same |
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