CN111048839A - Lithium ion battery electrolyte with good low-temperature discharge characteristic and lithium ion battery - Google Patents
Lithium ion battery electrolyte with good low-temperature discharge characteristic and lithium ion battery Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 56
- 239000003792 electrolyte Substances 0.000 title claims abstract description 47
- 239000000126 substance Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 14
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical class O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims abstract description 5
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000001923 cyclic compounds Chemical class 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 3
- 229910011297 LiCox Inorganic materials 0.000 claims description 3
- 229910013100 LiNix Inorganic materials 0.000 claims description 3
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 3
- 229910015818 MPO4 Inorganic materials 0.000 claims description 3
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 11
- FBPINGSGHKXIQA-UHFFFAOYSA-N 2-amino-3-(2-carboxyethylsulfanyl)propanoic acid Chemical compound OC(=O)C(N)CSCCC(O)=O FBPINGSGHKXIQA-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 102100028667 C-type lectin domain family 4 member A Human genes 0.000 description 1
- 101000766908 Homo sapiens C-type lectin domain family 4 member A Proteins 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910010941 LiFSI Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910012265 LiPO2F2 Inorganic materials 0.000 description 1
- AWIZPCJSRFJXCZ-UHFFFAOYSA-N N1C=CC=C1.S(=O)(=O)=O Chemical compound N1C=CC=C1.S(=O)(=O)=O AWIZPCJSRFJXCZ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 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
-
- 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
Abstract
The invention discloses a lithium ion battery electrolyte and a lithium ion battery with good low-temperature discharge characteristics, which comprise lithium salt, solvent and additive, wherein the additive comprises at least one vinylene carbonate derivative shown as a structural formula 1 and at least one complex shown as a chemical formula 2, and the complex is formed by the reaction of sulfur oxide and a nitrogen-containing heterocyclic compound; the lithium ion battery adopts the electrolyte of the invention. The prepared lithium ion battery electrolyte contains the compounds shown in the structural formula 1 and the chemical formula 2, so that the normal-temperature cycle performance and the low-temperature discharge rate of the lithium ion battery are improved, the battery impedance in a low-temperature environment is reduced, the low-temperature performance of the lithium ion battery is improved, and the use safety of the lithium ion battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery electrolyte and a lithium ion battery.
Background
With the development of new energy vehicles, power energy storage and high-performance digital products, people have higher requirements on the performance and the application range of batteries, and therefore lithium ion batteries capable of meeting the increasing requirements need to be developed. The electrolyte is an important component of the lithium ion battery, is called as 'blood' of the lithium ion battery, generally consists of lithium salt, solvent and additive, and has great influence on the cycle performance and the safety performance of the lithium ion battery.
When the lithium ion battery is in a low-temperature environment at present, the charge impedance of an SEI film is increased, so that the polarization of an electrode is increased in the charging and discharging process, electrolyte is decomposed and deposited on the surface of the electrode, the electrochemical performance of the battery is seriously deteriorated, and the product cannot be normally used and even explodes.
Therefore, under the condition of not changing the production process and the production cost of the lithium ion battery, the method for improving the low-temperature cycle performance of the battery is a simple and effective method by adding a small amount of additives into the electrolyte of the lithium ion battery.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a lithium ion battery electrolyte and a lithium ion battery with good low-temperature discharge characteristics, so as to solve the problems of large resistance and poor low-temperature performance of the lithium ion battery in a low-temperature environment, and further improve the discharge performance of the lithium ion battery under a low-temperature condition.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
Lithium ion battery electrolyte and lithium ion battery with good low temperature discharge characteristic, including lithium salt, solvent and additive, its characterized in that: the additive comprises at least one vinylene carbonate derivative shown as a structural formula 1 and at least one complex shown as a chemical formula 2, wherein the complex is formed by reacting sulfur oxide with a nitrogen-containing heterocyclic compound;
in the structural formula 1, R1 and R2 are any one of hydrogen atom, alkyl, alkoxy, halogen-containing alkyl and aryl respectively.
In the chemical formula 2, n is 2 or 3, and X is a five-membered ring or six-membered ring cyclic compound containing nitrogen.
According to the further optimized technical scheme, the cyclic compounds comprise the following compounds:
wherein, R3, R4, R5 and R6 are any of hydrogen atom, alkyl group, alkoxy group, halogen-containing alkyl group and aryl group.
According to a further optimized technical scheme, the complex is at least one of the following structural formulas:
the technical scheme is further optimized, wherein the total mass of the lithium ion battery electrolyte is 100%, the vinylene carbonate derivative shown as the structural formula 1 accounts for 0.1-5% of the total mass of the electrolyte solution, and the complex shown as the chemical formula 2 accounts for 0.01-5% of the total mass of the electrolyte solution.
According to a further optimized technical scheme, the additive also comprises a sultone compound accounting for 0.1-5% of the total mass of the electrolyte, and the sultone compound is at least one of 1, 3-propane sultone and 1, 4-butane sultone.
The invention also provides a lithium ion battery with good low-temperature discharge characteristics, which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and electrolyte, and is characterized in that: the electrolyte is the lithium ion battery electrolyte as defined in any one of claims 1 to 7.
Further optimizing the technical scheme, the anode material is LiNixCoyMnzL(1-x-y-z)O2、 LiCoxL(1-x’)O2、LiNixLyMn(2-x”-y’)O4And Liz’MPO4At least one of;
wherein L is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; m is at least one of Fe, Mn and Co;
0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0＜x’≤1，0.3＜x”≤0.6，0.01＜y’≤0.2， 0.5≤z’≤1。
due to the adoption of the technical scheme, the technical progress of the invention is as follows.
The electrolyte of the lithium ion battery respectively contains the compounds shown in the structural formula 1 and the chemical formula 2, the compound shown in the chemical formula 1 contains unsaturated bonds, and can be rapidly polymerized into a film at a negative electrode when the battery is charged and discharged, and the compound shown in the chemical formula 2 can react with a decomposition product of lithium salt to form a nitrogen-containing substance and a sulfur-containing substance to be attached to the surface of the negative electrode when the battery is charged and discharged, so that the composition of SEI is adjusted, and the impedance of the SEI is reduced.
Under the condition of not changing the production process and the production cost of the lithium ion battery, the stability of the cathode passivation film of the battery is ensured, the impedance and the low-temperature performance of the battery are effectively improved, and the use safety of the lithium ion battery is improved.
Detailed Description
The invention provides a lithium ion battery electrolyte with good low-temperature discharge characteristics, which can improve the discharge performance of a lithium ion battery under a low-temperature condition, and mainly comprises the following components: lithium salts, solvents and additives.
The additive comprises vinylene carbonate derivatives shown in a structural formula 1 and a complex shown in a chemical formula 2, wherein the complex is formed by reacting sulfur oxide with an oxygen-containing heterocyclic compound, and the complex also comprises sultone compounds. Wherein the vinylene carbonate derivative accounts for 0.1-5% of the total mass of the electrolyte solution, and a complex formed by the sulfur oxide and the nitrogen-containing heterocyclic compound accounts for 0.01-5% of the total mass of the electrolyte solution.
In the structural formula 1, R1 and R2 are each any of a hydrogen atom, an alkyl group, an alkoxy group, a halogen-containing alkyl group, and an aryl group.
In the chemical formula 2, n is 2 or 3, and X is a cyclic compound of the following types:
wherein, R3, R4, R5 and R6 are any of hydrogen atom, alkyl group, alkoxy group, halogen-containing alkyl group and aryl group.
Therefore, the complex corresponding to chemical formula 2 in the electrolyte is at least one of the following structural formulas:
the lithium ion battery electrolyte contains a compound in accordance with a structural formula 1 and a compound in accordance with a chemical formula 2, and the two functions simultaneously ensure the stability of a battery cathode passivation film and effectively improve the impedance and low-temperature performance of the battery.
The sultone compound is at least one of 1, 3-Propane Sultone (PS) and 1, 4-Butane Sultone (BS), and the sultone compound accounts for 0.1-5% of the total mass of the electrolyte solution.
The lithium salt comprises LiPF6And lithium salt additives accounting for 5.1-25% of the electrolyte; the lithium salt additive is LiBOB (lithium bis (oxalato) borate), LiFSI (lithium difluoro (oxalato) imide), LiODFB (lithium difluoro (oxalato) borate), LiBF4(lithium tetrafluoroborate) LiPO2F2(lithium difluorophosphate) and LiDFOP (lithium difluorobis (oxalato) phosphate).
The solvent is at least one of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and propyl methyl carbonate.
The invention provides a lithium ion battery with good low-temperature discharge characteristics, which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, and the lithium ion battery electrolyte provided by the invention; the anode material is LiNixCoyMnzL(1-x-y-z)O2、LiCoxL(1-x’)O2、LiNixLyMn(2-x”-y’)O4And Liz’MPO4Wherein L is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; m is at least one of Fe, Mn and Co;
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, x + y + z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0.3 and less than or equal to 0.6, y ' is more than or equal to 0.01 and less than or equal to 0.2, and z ' is more than or equal to 0..
The present invention will be described in further detail with reference to specific examples.
Example 1
The positive electrode used in the lithium ion battery in this embodiment is LiNi0.5Co0.2Mn0.3O2The negative electrode is artificial graphite, the diaphragm is a polyethylene microporous membrane, and the electrolyte is prepared by the method.
The electrolyte is prepared by mixing Ethylene Carbonate (EC) and Ethyl Methyl Carbonate (EMC): diethyl carbonate (DEC) ═ 3: 5: 2 (weight ratio) in the mixed solvent6Preparing 1mol/L solution, adding vinylene carbonate which accounts for 0.1 percent of the total weight of the electrolyte and accords with the structural formula 1, and adding a compound 2 which accounts for 0.01 percent of the total weight of the electrolyte, wherein the compound 2 is selected from pyridine-sulfur trioxide complex. The electrolyte solution thus prepared, and the associated positive and negative electrodes, separator, and the like were fabricated into the electrolyte solution secondary battery of example 1 in the manner described above.
Examples 2 to 16 and comparative examples 1 to 9
Examples 2 to 16 and comparative examples 1 to 9 were exactly the same as example 1 except that the amounts of the vinylene carbonate and the pyridine-sulfur trioxide complex in the electrolyte were adjusted. The amounts of ethylene carbonate and pyridine-sulfur trioxide complex in the specific examples are shown in table one.
Table 1:
the performance tests are respectively carried out on the embodiment and the comparative proportion, and the test indexes and the test method are as follows:
(1) the normal-temperature cycle performance is embodied by testing the capacity retention rate of 1C cycle N times at room temperature, and the specific method comprises the following steps:
the battery is placed in an environment of 45 ℃, and the formed battery is charged to 4.35V (LiNi) by using a 1C constant current and constant voltage0.5Co0.2Mn0.3O2Artificial graphite), the off current was 0.02C, and then the discharge was made to 3.0V with a constant current of 1C. After such charge/discharge cycles, the capacity retention rate after 100 weeks of cycling was calculated to evaluate the room temperature cycle performance.
The calculation formula of the capacity retention rate after 100 times of normal temperature circulation is as follows:
the 100 th cycle capacity retention (%) was (100 th cycle discharge capacity/1 st cycle discharge capacity) × 100%
(2) Battery impedance test-the battery after formation was charged to 4.35V (LiNi) with a 1C constant current and voltage0.5Co0.2Mn0.3O2Artificial graphite), the cutoff current was 0.02C, and then constant current discharge was performed to 3.0V with 1C, and the initial discharge capacity of the battery was measured. The discharge was then carried out at 1C to 50% capacity, and the discharge was carried out at 3C for 10s after leaving for 1 hour, and the value of the DC resistance DCIR was calculated.
(3) Low temperature discharge Rate-the cells after formation were charged to 4.35V (LiNi0.5Co) with a 1C constant current and constant voltage0.2Mn0.3O2Artificial graphite) and the cutoff current was 0.02C, and then the constant current was discharged to 3.0V with 1C, and the normal temperature discharge capacity of the cell was measured. The cell was charged at room temperature to 4.35V with a constant current and voltage of 1C and a cutoff current of 0.02C. The battery is cooled to-20 ℃, and after standing for 4 hours, the battery is discharged to 3.0V by using 0.2C current, so that the discharge capacity at low temperature is obtained.
-20 ℃ discharge capacity retention (%) (-20 ℃ discharge capacity/room temperature discharge capacity) × 100%
Examples 1 to 16 and comparative examples 1 to 9 were subjected to performance tests, respectively, and the results of the tests are shown in Table 2.
Table 2:
in the electrolytes of examples 1 to 16 and comparative examples 1 to 9, in which tables 1 and 2 are combined, the compositions of the lithium salt and the solvent in the electrolyte are the same in Ethylene Carbonate (EC): Ethyl Methyl Carbonate (EMC): diethyl carbonate (DEC) ═ 3: 5: 2 (weight ratio) of 1mol/L LiPF6Making into solution.
Examples 1-16 were grouped and compared with comparative examples 1-9: the comparative example 1 does not contain a compound conforming to the structural formula 1 or the chemical formula 2, the normal-temperature cycle retention rate of the lithium ion battery prepared from the electrolyte of the comparative example 1 is 28%, the direct-current impedance is 97m omega, and the low-temperature discharge rate at-20 ℃ is 56%; comparative examples 2 to 5 contain only pyridine-sulfur trioxide complex compounds conforming to the chemical formula 2, the normal temperature cycle retention of the lithium ion battery prepared by the electrolyte of the comparative examples 2 to 5 is slightly increased, the direct current impedance is slightly reduced, and the low-temperature discharge rate at-20 ℃ is obviously increased; comparative examples 6 to 9 contain only vinylene carbonate according to the structural formula 1, and the lithium ion battery prepared by the electrolyte of the comparative examples 6 to 9 has obviously increased normal-temperature cycle retention rate, slightly reduced direct-current impedance and slightly increased low-temperature discharge rate at-20 ℃. In the four groups of the electrolytes, the content of the vinylene carbonate is respectively 0.1%, 2.0%, 3.5% and 5.0%, and the normal-temperature cycle retention rate of the battery is increased along with the increase of the content of the vinylene carbonate; the content of the pyridine-sulfur trioxide complex of each embodiment in each group is 0.01%, 2.5%, 3.5% and 5.0% in sequence, and the low-temperature discharge rate of the battery at the temperature of-20 ℃ is increased along with the increase of the content of the pyridine-sulfur trioxide complex; under the combined action of vinylene carbonate and pyrrole-sulfur trioxide complex, the direct current impedance of the battery is greatly reduced.
The experimental results in Table 2 show that the batteries prepared from the electrolytes of examples 1-16 have a normal-temperature cycle retention rate as high as 92%, a low-temperature discharge rate at 20 ℃ as high as 89%, and direct-current impedance can be reduced to 41m omega.
Through testing the normal-temperature cycle performance, the low-temperature discharge capacity and the battery direct-current impedance of the lithium ion battery prepared by the embodiment, the lithium ion battery prepared by the electrolyte prepared by the invention has the advantages of high cycle retention rate, high low-temperature discharge rate and small direct-current impedance, the electrochemical performance of the lithium ion battery in a low-temperature environment can be effectively improved, and the use safety is improved.
Claims (9)
1. The lithium ion battery electrolyte with good low-temperature discharge characteristics comprises lithium salt, a solvent and an additive, and is characterized in that: the additive comprises at least one vinylene carbonate derivative shown as a structural formula 1 and at least one complex shown as a chemical formula 2, wherein the complex is formed by reacting sulfur oxide with a nitrogen-containing heterocyclic compound;
2. the lithium ion battery electrolyte having good low-temperature discharge characteristics according to claim 1, wherein: in the structural formula 1, R1 and R2 are any one of a hydrogen atom, an alkyl group, an alkoxy group, a halogen-containing alkyl group and an aryl group, respectively.
3. The lithium ion battery electrolyte having good low-temperature discharge characteristics according to claim 1, wherein: in the chemical formula 2, n is 2 or 3, and X is a five-membered ring or six-membered ring cyclic compound containing nitrogen.
4. The lithium ion battery electrolyte with good low-temperature discharge characteristics according to claim 3, wherein the cyclic compound comprises the following compounds:
wherein, R3, R4, R5 and R6 are any of hydrogen atom, alkyl group, alkoxy group, halogen-containing alkyl group and aryl group.
5. The lithium ion battery electrolyte having good low temperature discharge characteristics of claim 3 wherein the complex is at least one of the following structural formulas:
6. the lithium ion battery electrolyte with good low-temperature discharge characteristics according to claim 1, wherein the total mass of the lithium ion battery electrolyte is 100%, the vinylene carbonate derivative represented by the structural formula 1 accounts for 0.1-5% of the total mass of the electrolyte solution, and the complex represented by the chemical formula 2 accounts for 0.01-5% of the total mass of the electrolyte solution.
7. The lithium ion battery electrolyte with good low-temperature discharge characteristics according to claim 6, wherein the additive further comprises a sultone compound accounting for 0.1-5% of the total mass of the electrolyte, and the sultone compound is at least one of 1, 3-propane sultone and 1, 4-butane sultone.
8. Lithium ion battery with good low temperature discharge characteristic, including positive pole, negative pole, setting in positive pole with diaphragm between the negative pole to and electrolyte, its characterized in that: the electrolyte is the lithium ion battery electrolyte as defined in any one of claims 1 to 7.
9. The lithium ion battery having good low-temperature discharge characteristics according to claim 8, characterized in that: the positive electrode material is LiNixCoyMnzL(1-x-y-z)O2、LiCoxL(1-x’)O2、LiNixLyMn(2-x”-y’)O4And Liz’MPO4At least one of;
wherein L is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and Fe; m is at least one of Fe, Mn and Co;
0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0＜x’≤1，0.3＜x”≤0.6，0.01＜y’≤0.2，0.5≤z’≤1。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911359614.8A CN111048839A (en) | 2019-12-25 | 2019-12-25 | Lithium ion battery electrolyte with good low-temperature discharge characteristic and lithium ion battery |
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| CN111883841A (en) * | 2020-08-05 | 2020-11-03 | 香河昆仑化学制品有限公司 | Lithium ion battery non-aqueous electrolyte and lithium ion battery |
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Address after: 313103 South Industrial Functional Zone of Heping Town, Changxing County, Huzhou City, Zhejiang Province Applicant after: Huzhou Kunlun yienke battery material Co.,Ltd. Address before: 313103 South Industrial Functional Zone of Heping Town, Changxing County, Huzhou City, Zhejiang Province Applicant before: HUZHOU KUNLUN POWER BATTERY MATERIAL Co.,Ltd. |
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