CN111883838B - Nonaqueous electrolyte and lithium ion battery - Google Patents
Nonaqueous electrolyte and lithium ion battery Download PDFInfo
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- CN111883838B CN111883838B CN202010765678.4A CN202010765678A CN111883838B CN 111883838 B CN111883838 B CN 111883838B CN 202010765678 A CN202010765678 A CN 202010765678A CN 111883838 B CN111883838 B CN 111883838B
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 44
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 15
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- -1 cyclic carbonate compound Chemical class 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 239000003792 electrolyte Substances 0.000 claims description 46
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 16
- 229940125904 compound 1 Drugs 0.000 claims description 13
- 229940126214 compound 3 Drugs 0.000 claims description 13
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 229910013716 LiNi Inorganic materials 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 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
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims 1
- 229910013733 LiCo Inorganic materials 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 32
- 229910021383 artificial graphite Inorganic materials 0.000 description 28
- 150000003839 salts Chemical class 0.000 description 18
- 229910001290 LiPF6 Inorganic materials 0.000 description 17
- 239000000306 component Substances 0.000 description 15
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 9
- 239000000654 additive Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- DHKVCYCWBUNNQH-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,5,7-tetrahydropyrazolo[3,4-c]pyridin-6-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)C=NN2 DHKVCYCWBUNNQH-UHFFFAOYSA-N 0.000 description 1
- 229910013172 LiNixCoy Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- QJMYANXLHBZTKX-UHFFFAOYSA-N methanamine;sulfur trioxide Chemical compound NC.O=S(=O)=O QJMYANXLHBZTKX-UHFFFAOYSA-N 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
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
-
- 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
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- 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 discloses a nonaqueous electrolyte and a lithium ion battery. Comprises unsaturated cyclic carbonate compound and/or sultone compound, lithium salt, solvent, and compound shown in structural formula I. The non-aqueous electrolyte provided by the invention effectively improves the high-temperature cycle and high-temperature storage performance of the battery, and the lithium ion battery containing the non-aqueous electrolyte has excellent high-temperature cycle performance and high-temperature storage performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a non-aqueous electrolyte and a lithium ion battery.
Background
The power battery is a core component of a new energy automobile, the electrolyte is a key for restricting the development of the power battery, and the choice of the electrolyte basically determines the circulation, high temperature and low temperature safety performance of the battery. Additives are the core of value for electrolytes, which have a significant impact on electrolyte performance and are also key to the development of high performance electrolytes. With the current increasing demand for high energy density in power cells, there is an increasing demand for cell resistance, so there is an urgent need to develop related additives that can reduce the resistance of lithium ion cells.
Disclosure of Invention
The invention aims to provide a nonaqueous electrolyte and a lithium ion battery.
A nonaqueous electrolyte solution comprising an unsaturated cyclic carbonate compound and/or a sultone compound, a lithium salt, a solvent, and a compound represented by the structural formula I:
in the structural formula I, R1 is a C1-C6 alkyl group, and the C1-C6 group is selected from one of alkyl, fluoroalkyl, oxyalkyl and silane substituent; r2, R3, R4 and R5 are each independently selected from the group consisting of fluorohydrocarbyl, oxygenated hydrocarbyl, siliceous hydrocarbyl and cyano-substituted hydrocarbyl.
The structural formula I of the compound is selected from one or more of the following structures:
the name of the compound 1 is N-dimethyl-N-trimethylsilyl methylamine sulfur trioxide complex; compound 2 is named as N-dimethyl-N-dimethyl trifluoromethyl silyl methylamine sulfur trioxide complex; the name of the compound 3 is N-dimethyl-N-dimethyl methoxy silicon-based methylamine sulfur trioxide complex; compound 4 is named as N-methyl-N-trimethylsilyl-N-trimethylsilylmethylamine sulfur trioxide complex; compound 5 is named N-methyl-N-cyano-N-trimethylsilyl methylamine sulfur trioxide complex.
The mass percentage of the compound shown in the structural formula I is 0.1-5% based on 100% of the total mass of the nonaqueous electrolyte.
The unsaturated cyclic carbonate compound comprises at least one of ethylene carbonate and ethylene carbonate; the sultone compound comprises at least one of 1, 3-propane sultone and 1, 4-butane sultone.
Taking the total mass of the non-aqueous electrolyte as 100 percent, the mass percentage of the unsaturated cyclic carbonate compound is 0.1-5 percent; the mass percentage of the sultone compounds is 0.1-5%.
The lithium salt is LiPF 6 The content is 0.1-20%.
The solvent is at least one selected from ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate.
A lithium ion battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte; the electrolyte is the nonaqueous electrolyte according to any one of claims 1 to 7.
The positive electrode comprises an active material, and the active material of the positive electrode is LiNixCoy MnzL (1-x-y-z) O 2 、LiCoxL(1-x’)O 2 、LiNixLyMn(2-x”-y’),O4,Liz’MPO 4 At least one of (a) and (b); wherein L is at least one of Co, al, sr, mg, ti, ca, zr, zn, si, fe; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x+y+z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0 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 L ' is at least one of Co, al, sr, mg, ti, ca, zr, zn, si, fe; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x+y+z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0 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 L ' is at least one of Co, al, sr, mg, ti, ca, zr, zn, si, fe; and z' is more than or equal to 0.5 and less than or equal to 1, and M is at least one of Fe, mn and Co.
The invention has the beneficial effects that: the non-aqueous electrolyte provided by the invention effectively improves the high-temperature cycle and high-temperature storage performance of the battery, and the lithium ion battery containing the non-aqueous electrolyte has excellent high-temperature cycle performance and high-temperature storage performance.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 1 of Table 1 and 12% LiPF 6 And (3) salt.
Example 2
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte and the total weight of the nonaqueous electrolyte is 100%, comprising the components shown in example 2 of Table 1Component in mass percent and 12% LiPF 6 And (3) salt.
Example 3
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 3 of Table 1 and 12% LiPF 6 And (3) salt.
Example 4
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 4 of Table 1 and 12% LiPF 6 And (3) salt.
Example 5
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 5 of Table 1 and 12% LiPF 6 And (3) salt.
Example 6
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 6 of Table 1 and 12% LiPF 6 And (3) salt.
Example 7
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, comprising the components shown in example 7 of Table 1 in percentage by massIs a component of (2) and 12% LiPF 6 And (3) salt.
Example 8
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 8 of Table 1 and 12% LiPF 6 And (3) salt.
Example 9
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components having mass percentages shown in example 9 of Table 1 and 12% LiPF 6 And (3) salt.
Example 10
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components with mass percentages shown in example 10 of Table 1 and 12% LiPF 6 And (3) salt.
Comparative example 1
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components having mass percentages shown in comparative example 1 of Table 1 and 12% LiPF 6 And (3) salt.
Comparative example 2
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components having mass percentages shown in comparative example 2 of Table 1, and12％LiPF 6 and (3) salt.
Comparative example 3
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components having mass percentages shown in comparative example 3 of Table 1 and 12% LiPF 6 And (3) salt.
Comparative example 4
LiNi 0.5 Co 0.2 Mn 0.3 O 2 An artificial graphite battery comprising a positive electrode, a negative electrode, a separator, and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, the artificial graphite battery comprises components having mass percentages shown in comparative example 4 of Table 1 and 12% LiPF 6 And (3) salt.
TABLE 1
| Electrolyte salt and solvent composition | Additive and weight percentage content | |
| Example 1 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 1:1% |
| Example 2 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 1:3% |
| Example 3 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 3:1% |
| Example 4 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 3:3% |
| Example 5 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 1:1% of VC 1% |
| Example 6 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 3:1% of VC 1% |
| Example 7 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 1:1% PS 1% |
| Example 8 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 3:1%, PS:1% |
| Example 9 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 1:1%,1% VC,1% PS |
| Example 10 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | Compound 3:1%,1% VC,1% PS |
| Comparative example 1 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | |
| Comparative example 2 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | 1％VC |
| Comparative example 3 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | 1％PS |
| Comparative example 4 | 12％LiPF6,EC:DEC:EMC＝3:2:5(vol:vol) | 1％VC,1％PS |
The performance test, test index and test method of the invention of examples 1-10 and comparative examples 1-4 were as follows:
the high-temperature cycle performance is reflected by testing the capacity retention rate of 1C cycle for N times at 45 ℃, and the specific method is as follows: the battery after formation was charged to 4.35V (LiNi) with a constant current and a constant voltage of 1C at 45 DEG C 0.5 Co 0.2 Mn 0.3 O 2 Artificial graphite), the off-current was 0.02C, and then discharged to 3.0V with a constant current of 1C. After the charge/discharge cycle as such, the retention rate of the capacity after the cycle at week 200 was calculated to evaluate the high temperature cycle performance thereof.
The capacity retention rate after 200 cycles at 45℃was calculated as follows:
200 th cycle capacity retention (%) = (200 th cycle discharge capacity/1 st cycle discharge capacity) ×100%
The test method for the capacity retention rate, the capacity recovery rate and the thickness expansion rate after 30 days of storage at 60 ℃ comprises the following steps: the battery after formation is charged to 4.4V (LiNi) at normal temperature with 1C constant current and constant voltage 0.5 Co 0.2 Mn 0.3 O 2 The artificial graphite) is charged to 3.0V by using a constant current of 1C, the initial discharge capacity of the battery is measured, the initial thickness of the battery is measured by using a constant current of 1C to charge to 4.4V by using a constant current of 1C to charge to 0.01C, the thickness of the battery is measured after the battery is stored for 30 days at 60 ℃, the holding capacity of the battery is measured by using a constant current of 1C to charge to 3.0V, the battery is charged to 3.0V by using a constant current of 1C to charge to 0.02C by using a constant current of 1C, the recovery capacity is measured. The capacity retention rate, capacity recovery rate, and thickness expansion were calculated as follows:
battery capacity retention (%) =retention capacity/initial capacity ×100%
Battery capacity recovery rate (%) =recovery capacity/initial capacity ×100%
Cell thickness expansion (%) = (thickness after 30 days-initial thickness)/initial thickness × 100%
Cell thickness expansion (%) = (thickness after 30 days-initial thickness)/initial thickness × 100%
Experimental examples 1 to 10, and comparative examples 1 to 4 were tested as shown in table 2 below.
TABLE 2
In the lithium ion nonaqueous electrolytic solutions of comparative examples 1 to 2 and comparative example 1, and example 1 and comparative example 1, the electrolyte solvents and salts had the same composition (1.0M LiPF6,EC:DEC:EMC =3:2:5 (vol: vol)), but compound 1 was not present in the comparative example, by integrating tables 1 and 2. The test results showed that the discharge capacity maintenance rate performance and the impedance performance of the battery made by the electrolyte added with the compound 1 were remarkably improved, and the capacity maintenance rate after 200 weeks of circulation was as high as 87% and 82% (comparative example 1 was only 46%), and the impedance increase rate was 26% and 37% (comparative example 1 was 164%), as compared with the electrolyte without the compound 1 added. It can be seen that the compound 1 can significantly improve the cycle performance of the battery and reduce the impedance of the battery.
Comparative examples 3 to 4 and comparative example 1, the electrolyte solvents and salts had the same composition (1.0M LiPF6,EC:DEC:EMC =3:2:5 (vol: vol)) in the lithium ion nonaqueous electrolytic solutions of experimental examples 3 to 4 and comparative example 1, but no compound 3 was present in the comparative example. The test results showed that the discharge capacity maintenance performance and resistance storage performance of the battery made of the electrolyte to which the compound 3 was added were significantly improved, as compared with the electrolyte to which the compound 3 was not added, as high as 97% and 95% (comparative example 1 was only 46%) in capacity retention after 200 weeks, and as high as 26% and 37% (comparative example 1 was only 164%) in resistance increase. It can be seen that the compound 3 can significantly improve the cycle performance of the battery and reduce the impedance of the battery.
Comparative examples 5 to 10 and comparative examples 2 to 4 have the same composition ratio of electrolyte solvent and salt as 1.0M LiPF6,EC:DEC:EMC =3:2:5 (vol: vol)), and are increased by the same amounts of VC and PS, respectively. However, in comparative examples 2 to 4, compound 1 or compound 3 was not added. The battery test results show that compared with comparative examples 2 to 4, the discharge capacity maintenance performance and the impedance performance of the battery prepared from the nonaqueous electrolyte solution of the lithium ion battery of example 6 are obviously improved. Up to 94% (comparative example 2 only 76%) after 200 weeks of cycling, the impedance increase was only 21% (comparative example up to 87%).
The analysis of the action mechanism of the additive shows that the sulfur element group contained in the additive can form SEI film with lower impedance, and the Si-containing group can remove water and HF in the electrolyte, so that the formed SEI impedance can be reduced, the impedance of the whole battery is lower, and better cycle performance can be maintained.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (8)
1. A nonaqueous electrolytic solution comprising an unsaturated cyclic carbonate compound and/or a sultone compound, a lithium salt, a solvent, and compound 1 or compound 3:
2. the nonaqueous electrolytic solution according to claim 1, wherein the mass percentage of the compound 1 or the compound 3 is 0.1 to 5% based on 100% of the total mass of the nonaqueous electrolytic solution.
3. The nonaqueous electrolytic solution according to claim 1, wherein the unsaturated cyclic carbonate compound comprises at least one of vinylene carbonate and ethylene carbonate; the sultone compound comprises at least one of 1, 3-propane sultone and 1, 4-butane sultone.
4. The nonaqueous electrolytic solution according to claim 1, wherein the unsaturated cyclic carbonate compound is present in an amount of 0.1 to 5% by mass based on 100% by mass of the total nonaqueous electrolytic solution; the mass percentage of the sultone compounds is 0.1-5%.
5. The nonaqueous electrolyte according to claim 1, wherein the lithium salt is LiPF 6 The content is 0.1-20%.
6. The nonaqueous electrolytic solution according to claim 1, wherein the solvent is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and methylpropyl carbonate.
7. A lithium ion battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte; the electrolyte is the nonaqueous electrolyte according to any one of claims 1 to 6.
8. The lithium ion battery of claim 7, wherein the positive electrode comprises an active material, and the active material of the positive electrode is LiNi x Co y Mn z L (1-x-y-z) O 2 、LiCo x’ L (1-x’) O 2 、LiNi x“ L’ y' Mn (2-x’’-y’) O4,Li z’ MPO 4 At least one of (a) and (b); wherein L is at least one of Al, sr, mg, ti, ca, zr, zn, si, fe; x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x+y+z is more than or equal to 0 and less than or equal to 1, x ' is more than or equal to 0 and less 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 L ' is at least one of Co, al, sr, mg, ti, ca, zr, zn, si, fe; and z' is more than or equal to 0.5 and less than or equal to 1, and M is at least one of Fe, mn and Co.
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