CN111244545B - Overcharge-preventing electrolyte and lithium ion battery using same - Google Patents
Overcharge-preventing electrolyte and lithium ion battery using same Download PDFInfo
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- CN111244545B CN111244545B CN202010067825.0A CN202010067825A CN111244545B CN 111244545 B CN111244545 B CN 111244545B CN 202010067825 A CN202010067825 A CN 202010067825A CN 111244545 B CN111244545 B CN 111244545B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 45
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 45
- 230000000996 additive effect Effects 0.000 claims abstract description 39
- -1 sulfonyl imidazole compound Chemical class 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- YZYKZHPNRDIPFA-UHFFFAOYSA-N tris(trimethylsilyl) borate Chemical compound C[Si](C)(C)OB(O[Si](C)(C)C)O[Si](C)(C)C YZYKZHPNRDIPFA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 6
- MCNQDGXBYQRUGL-UHFFFAOYSA-N 2-sulfonylimidazole Chemical class O=S(=O)=C1N=CC=N1 MCNQDGXBYQRUGL-UHFFFAOYSA-N 0.000 claims description 5
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- ALGVJKNIAOBBBJ-UHFFFAOYSA-N 3-[2,3-bis(2-cyanoethoxy)propoxy]propanenitrile Chemical compound N#CCCOCC(OCCC#N)COCCC#N ALGVJKNIAOBBBJ-UHFFFAOYSA-N 0.000 claims description 2
- VTHRQKSLPFJQHN-UHFFFAOYSA-N 3-[2-(2-cyanoethoxy)ethoxy]propanenitrile Chemical compound N#CCCOCCOCCC#N VTHRQKSLPFJQHN-UHFFFAOYSA-N 0.000 claims description 2
- OOWFYDWAMOKVSF-UHFFFAOYSA-N 3-methoxypropanenitrile Chemical compound COCCC#N OOWFYDWAMOKVSF-UHFFFAOYSA-N 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 abstract description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 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
- 239000011884 anode binding agent Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides an overcharge-preventing electrolyte and a lithium ion battery using the same. The electrolyte comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a sulfonyl imidazole compound shown in a formula 1, a positive electrode protection additive and a low-impedance additive; wherein the positive electrode protection additive is selected from nitrile compounds; the low impedance additive is selected from at least one of tris (trimethylsilyl) borate (TMSB), ethylene sulfate, lithium difluorophosphate and lithium tetrafluoroborate; the electrolyte can well solve the safety problem caused by overcharge and overdischarge of the conventional lithium ion battery, and the lithium ion battery using the electrolyte has excellent overcharge performance, good safety performance and high and low temperature charge and discharge performance.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to an overcharge-preventing electrolyte and a lithium ion battery using the electrolyte.
Background
Since commercialization, lithium ion batteries have been widely used in the fields of digital, energy storage, power, military aerospace, and communication equipment, due to their high specific energy and good cycle performance. With the wide application of lithium ion batteries, the use environment and demand of consumers for lithium ion batteries are continuously increasing, which requires that the lithium ion batteries have the characteristics of high and low temperature performance. Meanwhile, the lithium ion battery has a serious safety problem in the use process, and when the battery is overcharged, overdischarged or in some extreme use conditions, potential safety hazards are easy to generate, and fire or even explosion occurs.
The electrolyte is used as an important component of the lithium ion battery and has great influence on the performance of the battery. In order to solve these problems, safety performance can be improved by adding overcharge protection additives (e.g., biphenyl, cyclohexylbenzene, etc.) to the electrolyte, but the ability to suppress overcharge is limited when the amount of these additives is small, and battery performance is seriously deteriorated when the amount is large. Therefore, the development of an electrolyte for a lithium ion battery, which can protect the battery from overcharge without affecting the electrochemical performance of the battery, is urgently needed at present.
Disclosure of Invention
The invention aims to solve the safety problem caused by overcharge and overdischarge of the conventional lithium ion battery, and provides an overcharge-preventing electrolyte and a lithium ion battery using the electrolyte.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an electrolyte comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a sulfonyl imidazole compound shown as a formula 1, a positive electrode protection additive and a low-impedance additive;
wherein the positive electrode protection additive is selected from nitrile compounds;
the low impedance additive is selected from at least one of tris (trimethylsilyl) borate (TMSB), ethylene sulfate, lithium difluorophosphate and lithium tetrafluoroborate;
in the formula 1, R1Selected from substituted or unsubstituted C1-C10Alkyl, pyrazolyl, pyrrolidinyl,Pyridyl, imidazolyl, substituted or unsubstituted C6-C10Aryl, said substituted group being selected from alkyl or halogen.
Preferably, in formula 1, R1Selected from imidazolyl, substituted or unsubstituted C1-C6Alkyl, substituted or unsubstituted C6-C10Aryl, said substituted group being selected from C1-C6Alkyl or halogen.
According to the invention, the sulfonyl imidazole compound shown in the formula 1 is selected from at least one of the following compounds:
according to the invention, the usage amount of the sulfonyl imidazole compound shown in the formula 1 accounts for 0.01-2 wt% of the total mass of the electrolyte. For example, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%.
According to the invention, the nitrile compound is selected from at least one of 3-methoxypropionitrile, Adiponitrile (ADN), ethylene glycol bis (propionitrile) ether, 1,3, 6-Hexanetrinitrile (HTCN) and 1,2, 3-tris- (2-cyanoethoxy) propane.
According to the invention, the usage amount of the positive electrode protection additive accounts for 2-8 wt% of the total mass of the electrolyte. For example 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.% or 8 wt.%.
According to the invention, the low impedance additive is preferably tris (trimethylsilyl) borate.
According to the invention, the low-impedance additive is used in an amount of 0.01 to 2 wt% based on the total mass of the electrolyte. For example, 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.2 wt%, 1.5 wt%, 2 wt%.
According to the present invention, the organic solvent is selected from a mixture of at least one of cyclic carbonates and at least one of linear carbonates and linear carboxylates in an arbitrary ratio.
Preferably, the cyclic carbonate is at least one selected from ethylene carbonate and propylene carbonate, the linear carbonate is at least one selected from dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and the linear carboxylate is at least one selected from ethyl propionate, propyl propionate and propyl acetate.
According to the invention, the organic solvent accounts for 100 percent of the total mass, wherein the mass fraction of the cyclic carbonate is 15 to 40wt percent, and the mass fraction of the linear carbonate and/or the linear carboxylic ester is 60 to 85wt percent.
Preferably, the organic solvent accounts for 100 percent of the total mass, wherein the mass fraction of the linear carboxylic ester is 30 to 60 weight percent.
In the electrolyte, the sulfonyl imidazole compound shown in the formula 1 can be subjected to ring-opening polymerization on the surface of a positive electrode to form a passivation film, meanwhile, the anode protective additive can be complexed with the anode metal ions to form a protective film, the synergistic effect of the anode protective additive and the anode metal ions reduces the side reaction of the anode and the electrolyte, improves the stability of the anode material, the protective film formed by the two layers plays a role of preventing overcharge for the anode under the overcharge condition, thereby improving the safety performance of the battery, however, the sulfonyl imidazole compounds shown in the formula 1 can also form an SEI film with relatively high impedance on a negative electrode interface, so that the low-impedance additive added into the electrolyte can preferentially form a stable SEI film with high ionic conductivity on the surface of a negative electrode, the sulfonyl imidazole compounds shown in the formula 1 are inhibited from forming a film on the negative electrode, the adverse effect of the sulfonyl imidazole compounds on the high-low temperature charge and discharge performance of the battery is reduced, and the overcharge performance of the battery can be obviously improved.
The invention also provides a preparation method of the electrolyte, which comprises the following steps:
and mixing an organic solvent, a lithium salt and the additive to prepare the electrolyte.
According to the invention, the mixing is not limited by the order of addition.
The invention also provides a lithium ion battery which comprises the electrolyte.
According to the invention, the lithium ion battery also comprises a positive plate, a negative plate and a diaphragm, wherein the diaphragm is arranged between the positive plate and the negative plate. The diaphragm arranged between the positive plate and the negative plate can prevent the current short circuit caused by the contact of the two plates and can allow lithium ions to pass through.
According to the present invention, the anode includes an anode current collector and an anode active material layer disposed on one or both surfaces of the anode current collector.
Wherein, the negative current collector is selected from copper foil, such as electrolytic copper foil or rolled copper foil.
Wherein the anode active material layer includes an anode active material and an anode binder.
According to the present invention, the negative active material may be one or more of graphite, a silicon material, a silicon-carbon composite material, a silica material, an alloy material, and a lithium-containing metal composite oxide material.
According to the present invention, the positive electrode includes a positive electrode current collector and a positive electrode active material layer provided on one or both surfaces of the positive electrode current collector.
Wherein the positive electrode current collector is selected from aluminum foil.
Wherein the positive electrode active material layer includes a positive electrode active material and a positive electrode binder.
According to the present invention, the positive electrode active material is a lithium-containing compound. The lithium-containing compound includes one or more of a lithium transition metal composite oxide and a lithium transition metal phosphate compound.
According to the present invention, the positive electrode active material has a compacted density of 3.8 to 4.4mg/cm when applied3The negative electrode active material has a compacted density of 1.5 to 1.9mg/cm when applied3。
According to the invention, the separator is selected from porous films.
Wherein, the diaphragm is a porous film made of polymer.
The invention has the beneficial effects that:
the invention provides an overcharge-preventing electrolyte and a lithium ion battery using the same. The electrolyte comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a sulfonyl imidazole compound shown in a formula 1, a positive electrode protection additive and a low-impedance additive; wherein the positive electrode protection additive is selected from nitrile compounds; the low impedance additive is selected from at least one of tris (trimethylsilyl) borate (TMSB), ethylene sulfate, lithium difluorophosphate and lithium tetrafluoroborate; the electrolyte can well solve the safety problem caused by overcharge and overdischarge of the conventional lithium ion battery, and the lithium ion battery using the electrolyte has excellent overcharge prevention performance, good safety performance and high and low temperature charge and discharge performance.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The structural formula of the compound represented by formula 1 involved in the following examples and comparative examples is as follows:
comparative example 1
The solvents ethylene carbonate/propylene carbonate/diethyl carbonate/propyl propionate were mixed at a mass ratio of 20:15:20:45, 0.5 wt% of TMSB was added to the mixed solution as an additive, based on the total mass of the electrolyte, and finally 1mol/L of lithium hexafluorophosphate was added to obtain the electrolyte of comparative example 1.
And injecting the electrolyte into the battery cell which contains the positive plate, the negative plate and the diaphragm and is not injected with liquid to prepare the lithium ion battery, thus obtaining the battery of the comparative example 1.
Example 1
The solvents ethylene carbonate/propylene carbonate/diethyl carbonate/propyl propionate were mixed at a mass ratio of 20:15:20:45, and 0.8 wt% of T1, 0.5 wt% of TMSB and 3 wt% of ADN were added to the mixed solution as additives, based on the total mass of the electrolyte, and finally 1mol/L of lithium hexafluorophosphate was added to obtain the electrolyte of example 1.
The electrolyte was injected into an uninjected cell containing a positive electrode sheet, a negative electrode sheet, and a separator to prepare a lithium ion battery, and the battery of example 1 was obtained.
Comparative examples 2 to 6 and examples 2 to 12
Comparative examples 2 to 6 differ from comparative example 1 above only in the selected amounts of additives, as shown in table 1 below, and examples 2 to 12 differ from example 1 above only in the selection and amount of solvent, and the selected amounts of additives, as shown in table 1 below:
TABLE 1 compositions of electrolytes prepared in examples and comparative examples
The lithium ion batteries obtained in the above comparative examples and examples were subjected to electrochemical performance tests:
overcharge experiment:
the cells obtained in the examples and comparative examples were constant-current charged at 3C rate to 5V recording cell state.
High temperature cycling experiment at 55 ℃:
placing the batteries obtained in the examples and the comparative examples in an environment of (55 +/-2) DEG C, standing for 2-3 hours, when the battery body reaches (55 +/-2) DEG C, keeping the cut-off current of the battery at 0.05C according to 1C constant current charging, standing for 5 minutes after the battery is fully charged, then discharging to the cut-off voltage of 3.0V at 0.7C constant current, recording the highest discharge capacity of the previous 3 cycles as an initial capacity Q, and when the cycles reach the required times, recording the last discharge capacity Q1 of the battery; and recording the initial thickness T of the battery cell, and recording the thickness T0 when the battery cell is selected and circulated to 300 weeks. The results are reported in Table 2.
The calculation formula used therein is as follows:
capacity retention (%) ═ Q1/Q × 100%;
the thickness change ratio (%) - (T0-T)/T × 100%.
10 ℃ low temperature cycling experiment:
placing the batteries obtained in the examples and the comparative examples in an environment of (10 +/-2) DEG C, standing for 2-3 hours, when the battery body reaches (10 +/-2) DEG C, keeping the cut-off current of the battery at 0.7C constant current charging at 0.05C, standing for 5 minutes after the battery is fully charged, then discharging to the cut-off voltage of 3.0V at 0.5C constant current, recording the highest discharge capacity of the previous 3 cycles as an initial capacity Q2, and when the cycles reach the required times, recording the last discharge capacity Q3 of the battery; and recording the initial thickness T1 of the battery cell, and recording the thickness of the battery cell after the battery cell is cycled to 300 weeks as T2. The results are reported in Table 2.
The calculation formula used therein is as follows:
capacity retention rate (%) ═ Q3/Q2 × 100%;
the thickness change ratio (%) - (T2-T1)/T × 100%.
High temperature storage at 60 ℃ for 30 days experiment:
the batteries obtained in the examples and comparative examples were subjected to a charge-discharge cycle test at room temperature for 3 times at a charge-discharge rate of 0.5C, and then the 0.5C rate was charged to a full state, and the maximum discharge capacity Q4 and the battery thickness T3 were recorded for the previous 3 times of 0.5C cycles, respectively. The battery in a full charge state is stored for 30 days at 60 ℃, the thickness T4 of the battery and the discharge capacity Q5 of 0.5C after 6 hours are recorded, experimental data such as the thickness change rate, the capacity retention rate and the like of the battery stored at high temperature are obtained through calculation, and the recording results are shown in table 2.
The calculation formula used therein is as follows:
thickness change rate (%) (T4-T3)/T3 × 100%;
capacity retention (%) ═ Q5/Q4 × 100%.
Table 2 comparison of experimental results of batteries prepared in examples and comparative examples
Note that "explosion (1/5)" in the above table means that only one battery passes through and the remaining 4 batteries explode.
As can be seen from table 2: the lithium ion battery using the electrolyte has excellent overcharge performance, good safety performance and high and low temperature charge and discharge performance. In particular, it can be seen from example 1 and comparative examples 1 to 6 that the combination of the compound shown in formula 1 and the nitrile additive can significantly improve the overcharge performance of the lithium ion battery, this is mainly because the sulfonyl imidazole compounds represented by formula 1 can form a passivation film on the surface of the positive electrode by ring-opening polymerization, meanwhile, the anode protective additive can be complexed with the anode metal ions to form a protective film, the synergistic effect of the anode protective additive and the anode metal ions plays a role in preventing overcharge of the anode, however, the sulfonyl imidazole compound shown in formula 1 can also form an SEI film with relatively high impedance on a negative electrode interface, and the electrolyte of the invention can preferentially form a stable SEI film with high ionic conductivity on the surface of a negative electrode by adding the SEI film, so that the low-impedance additive formed by the sulfonyl imidazole compound shown in formula 1 on the negative electrode is inhibited, the adverse effect of the low-impedance additive on the performance of the battery is reduced, the overcharge performance of the battery is remarkably improved, and the excellent electrochemical performance is maintained. From the examples, the results of examples 4, 7, 9 and 10 are all better, which mainly aims to further improve the electrochemical performance of the battery by optimizing the amount of different additives under the condition of ensuring the overcharge performance.
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, or improvement 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 comprises an organic solvent, lithium salt and an additive, wherein the additive comprises a sulfonyl imidazole compound shown as a formula 1, a positive electrode protection additive and a low-impedance additive;
wherein the positive electrode protection additive is selected from nitrile compounds; the nitrile compound is at least one selected from the group consisting of 3-methoxypropionitrile, adiponitrile, ethylene glycol bis (propionitrile) ether, 1,3, 6-hexanetrinitrile, and 1,2, 3-tris- (2-cyanoethoxy) propane;
the low impedance additive is selected from at least one of tris (trimethylsilyl) borate and ethylene sulfate;
formula 1
In the formula 1, R1Selected from substituted or unsubstituted C6-C10Aryl, substituted group is selected from alkyl or halogen.
2. The electrolyte of claim 1, wherein in formula 1, the substituted group is selected from C1-C6An alkyl group.
3. The electrolyte solution according to claim 2, wherein the sulfonyl imidazole compound represented by formula 1 is at least one selected from the following compounds:
formula T4
Formula T5.
4. The electrolyte solution according to claim 1, wherein the sulfonyl imidazole compounds represented by formula 1 are used in an amount of 0.01 to 2 wt% based on the total mass of the electrolyte solution.
5. The electrolyte of claim 1, wherein the positive electrode protective additive is used in an amount of 2 to 8 wt% based on the total mass of the electrolyte.
6. The electrolyte of claim 1, wherein the low impedance additive is used in an amount of 0.01 to 2 wt% based on the total mass of the electrolyte.
7. The electrolytic solution according to any one of claims 1 to 6, wherein the organic solvent is selected from a mixture of at least one of cyclic carbonates and at least one of linear carbonates and linear carboxylates, in any proportion;
wherein, the cyclic carbonate is selected from at least one of ethylene carbonate and propylene carbonate, the linear carbonate is selected from at least one of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate, and the linear carboxylate is selected from at least one of ethyl propionate, propyl propionate and propyl acetate.
8. The electrolyte as claimed in claim 7, wherein the organic solvent is 100% by mass, wherein the cyclic carbonate is 15 to 40 wt% by mass, and the linear carbonate and/or the linear carboxylic ester is 60 to 85 wt% by mass.
9. The electrolyte as claimed in claim 8, wherein the organic solvent is 100% by mass in total, and wherein the linear carboxylic acid ester is present in an amount of 30 to 60 wt%.
10. A lithium ion battery comprising the electrolyte of any of claims 1-9.
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| CN114373987B (en) * | 2020-10-15 | 2024-04-19 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| CN112467219B (en) * | 2020-12-03 | 2022-03-29 | 珠海冠宇电池股份有限公司 | Electrolyte and lithium ion battery comprising same |
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