CN111883836A - Non-aqueous electrolyte of lithium ion battery and lithium ion battery - Google Patents
Non-aqueous electrolyte of lithium ion battery and lithium ion battery Download PDFInfo
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- CN111883836A CN111883836A CN202010728485.1A CN202010728485A CN111883836A CN 111883836 A CN111883836 A CN 111883836A CN 202010728485 A CN202010728485 A CN 202010728485A CN 111883836 A CN111883836 A CN 111883836A
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- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 87
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 239000000654 additive Substances 0.000 claims abstract description 27
- 230000000996 additive effect Effects 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims description 44
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 19
- 229910003002 lithium salt Inorganic materials 0.000 claims description 12
- 159000000002 lithium salts Chemical class 0.000 claims description 12
- -1 cyclic carbonate ester compounds Chemical class 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- 125000002560 nitrile group Chemical group 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-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 description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910011297 LiCox Inorganic materials 0.000 claims description 2
- 229910013100 LiNix Inorganic materials 0.000 claims description 2
- 229910013172 LiNixCoy Inorganic materials 0.000 claims description 2
- 229910012265 LiPO2F2 Inorganic materials 0.000 claims description 2
- 229910015818 MPO4 Inorganic materials 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-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
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims 1
- 229910010941 LiFSI Inorganic materials 0.000 claims 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 16
- 238000011084 recovery Methods 0.000 abstract description 9
- 238000005562 fading Methods 0.000 abstract description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 38
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 241001116500 Taxus Species 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 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
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 150000008053 sultones Chemical class 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- 241000158748 Acronychia Species 0.000 description 1
- 235000001453 Glycyrrhiza echinata Nutrition 0.000 description 1
- 244000303040 Glycyrrhiza glabra Species 0.000 description 1
- 235000006200 Glycyrrhiza glabra Nutrition 0.000 description 1
- 235000017382 Glycyrrhiza lepidota Nutrition 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 229940010454 licorice Drugs 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/002—Inorganic 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)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium ion battery non-aqueous electrolyte and a lithium ion battery, wherein the lithium ion battery non-aqueous electrolyte comprises a compound additive with a structure shown in a formula I, the additive can enable the capacity retention rate of the lithium ion battery to be more than 73% after 200 times of 45-DEG C circulation, the capacity retention rate to be more than 72%, the capacity recovery rate to be more than 74% and the thick expansion rate to be less than 30% after the lithium ion battery is stored for 30 days at a high temperature of 60 ℃, and the problems of too fast capacity fading and severe high-temperature ballooning of the current lithium ion battery non-aqueous electrolyte in circulation are solved.
Description
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a lithium ion battery non-aqueous 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 and higher requirements on the performance and the application range of batteries, and therefore lithium ion batteries which can meet the increasing demands need to be developed. This is particularly important to improve the cycle life and temperature suitability of the battery.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a lithium ion battery nonaqueous electrolyte and a lithium ion battery. The lithium ion battery non-aqueous electrolyte can solve the problems of too fast capacity fading of the cycle of the conventional lithium ion battery non-aqueous electrolyte and severe high-temperature ballooning.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a lithium ion battery nonaqueous electrolyte, which includes a compound additive with a structure shown in formula I below:
wherein R is a nitrile group, a nitrile group substituted C1-C4 (e.g., C1, C2, C3, or C4) hydrocarbyl group.
In the invention, the compound is used as an additive, wherein the existence of a cyano group has good stability on a positive electrode, strong oxidation resistance and good coordination capacity, and the cyano group can be combined with active sites on the surface of an electrode to reduce the oxidative decomposition of an electrolyte, so that the cycle performance and the high-temperature storage performance of the lithium ion battery can be effectively improved.
Preferably, the compound additive is selected from any one of or a combination of at least two of the compounds represented by the following structures:
In the present invention, the compound additive represented by formula I is synthesized as follows:
the first step of reaction:
the first step reaction conditions are high temperature 50 deg.C-120 deg.C (e.g., 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C, 110 deg.C or 120 deg.C).
The second step of reaction:
the second reaction conditions should be carried out in triethylamine solvent.
The third step of reaction:
and thirdly, reaction conditions are normal temperature.
Preferably, the compound additive represented by the formula I is contained in an amount of 0.1 to 5% by mass, for example, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5% or 5%, preferably 1 to 3% by mass, based on 100% by mass of the total mass of the lithium ion battery nonaqueous electrolyte solution.
Preferably, the solvent in the non-aqueous electrolyte of the lithium ion battery is selected from any one of Ethylene Carbonate (EC), Propylene Carbonate (PC), Butylene Carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC) or Methyl Propyl Carbonate (MPC) or a combination of at least two thereof.
Preferably, the lithium ion battery non-aqueous electrolyte further comprises other additives besides the compound additive shown in the formula I.
Preferably, the other additive includes at least one of an unsaturated cyclic carbonate-based compound or a sultone-based compound.
Preferably, the unsaturated cyclic carbonate-based compound includes at least one of vinylene carbonate (abbreviated as VC) and vinyl ethylene carbonate (abbreviated as VEC).
Preferably, the sultone compound comprises at least one of 1, 3-Propane Sultone (PS) and 1, 4-butane sultone.
Preferably, the unsaturated cyclic carbonate compound is contained in an amount of 0.1 to 5% by mass, for example, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5% or 5% by mass based on 100% by mass of the total amount of the lithium ion battery nonaqueous electrolyte solution.
Preferably, the content of the sultone-based compound is 0.1 to 5% by mass, for example, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5% or 5% by mass based on 100% by mass of the total mass of the nonaqueous electrolyte solution for a lithium ion battery.
Preferably, the other additives further include lithium salt additives, and the lithium salt additives include LiBOB (bis (oxalato) borate), LiFSi (lithium difluorosulfonato imide), LiODFB (lithium difluorooxalato borate), and LiBF4(lithium tetrafluoroborate) LiPO2F2(lithium difluorophosphate) or LiDFOP (lithium difluorobis (oxalato) phosphate), or a combination of at least two of them.
Preferably, the lithium salt-based additive is contained in an amount of 0.1 to 5% by mass, for example, 0.5%, 0.8%, 1%, 1.5%, 1.8%, 2%, 2.5%, 2.8%, 3%, 3.5%, 3.8%, 4%, 4.5% or 5% by mass based on 100% by mass of the total amount of the lithium ion battery nonaqueous electrolyte solution.
Preferably, the electrolyte in the non-aqueous electrolyte of the lithium ion battery is a lithium salt, and the lithium salt is preferably LiPF6。
Preferably, the content of the electrolyte lithium salt in the non-aqueous electrolyte solution of the lithium ion battery is 0.1 to 20% by mass, for example, 0.5%, 0.8%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12%, 14%, 16%, 18% or 20%.
In another aspect, the present invention provides 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 solution, wherein the electrolyte solution is the lithium ion battery non-aqueous electrolyte solution described above.
Preferably, the positive electrode includes an active material that is LiNixCoyMnzL(1-x-y-z)O2、LiCoxL(1-x')O2、LiNixLyMn(2-x”-y')O4Liz'MPO4At least one of; wherein L is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and 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 0 and less than or equal to 1, x ' is more than 0.3 and less than or equal to 0.6, y ' is more than 0.01 and less than or equal to 0.2, 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.
In the present invention, the positive electrode, the negative electrode, and the separator are not particularly limited, and any of the positive electrode, the negative electrode, and the separator that are conventional in the art can be used.
The lithium ion battery non-aqueous electrolyte provided by the invention effectively improves the cycle and high-temperature storage performance of the battery, and the lithium ion battery containing the non-aqueous electrolyte has excellent cycle performance and high-temperature storage performance.
Compared with the prior art, the invention has the following beneficial effects:
the compound additive shown in the formula I is used in the lithium ion battery non-aqueous electrolyte, wherein the existence of the cyano group has good stability on the positive electrode, strong oxidation resistance and good coordination capacity, and the cyano group can be combined with active sites on the surface of an electrode, so that the oxidative decomposition of the electrolyte is reduced, and the cycle performance and the high-temperature storage performance of the lithium ion battery can be effectively improved. The capacity retention rate of the lithium ion battery can be more than 73% after 200 times of 45 ℃ circulation, the capacity retention rate is more than 72%, the capacity recovery rate is more than 74%, the thick expansion rate is less than 30% after the lithium ion battery is stored for 30 days at a high temperature of 60 ℃, and the lithium ion battery has a wide market application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a diaphragm (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentages shown in example 1 in Table 1 and 12% of LiPF6And (3) salt.
Example 2
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentages shown in example 2 in Table 1 and 12% of LiPF6And (3) salt.
Example 3
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a diaphragm (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 3 in Table 1 and 12% of LiPF6And (3) salt.
Example 4
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 4 in Table 1 and 12% of LiPF6And (3) salt.
Example 5
LiNi0.5Co0.2Mn0.3O2Artificial graphite electricityA cell comprising a positive electrode (NCM523 from allied Licorice), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Haemarginia), and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, and the total weight of the non-aqueous electrolyte is 100%, and comprises the components in the mass percentages shown in example 5 of Table 1 and 12% of LiPF6And (3) salt.
Example 6
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 6 in Table 1 and 12% of LiPF6And (3) salt.
Example 7
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentages shown in example 7 in Table 1 and 12% of LiPF6And (3) salt.
Example 8
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 8 in Table 1 and 12% of LiPF6And (3) salt.
Example 9
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Acronychia), and an electrolyte, wherein the electrolyte is non-aqueous electrolyteA nonaqueous electrolyte solution containing the components in the mass percentages shown in example 9 of Table 1 and 12% of LiPF, wherein the total weight of the nonaqueous electrolyte solution is 100%6And (3) salt.
Example 10
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 10 of Table 1 and 12% of LiPF6And (3) salt.
Example 11
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentages shown in example 11 of Table 1 and 12% of LiPF6And (3) salt.
Example 12
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 12 in Table 1 and 12% of LiPF6And (3) salt.
Example 13
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 13 in Table 1 and 12% of LiPF6And (3) salt.
Example 14
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprises a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from fir), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, the total weight of the nonaqueous electrolyte is 100%, and the nonaqueous electrolyte contains the components with the mass percentage shown in example 14 of Table 1 and 12% of LiPF6And (3) salt.
Comparative example 1
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprising a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from Taxus), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, and the battery comprises the components in the mass percentages shown in comparative example 1 in Table 1 and 12% of LiPF6And (3) salt.
Comparative example 2
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprising a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from Taxus), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, and the battery comprises the components in the mass percentages shown in comparative example 2 in Table 1 and 12% of LiPF6And (3) salt.
Comparative example 3
LiNi0.5Co0.2Mn0.3O2An artificial graphite battery comprising a positive electrode (NCM523 from Union, Confucius), a negative electrode (artificial graphite P15 from Taxus), a separator (PP/PE from Hakko), and an electrolyte, wherein the electrolyte is a nonaqueous electrolyte, and the total weight of the nonaqueous electrolyte is 100%, and the battery comprises the components in the mass percentages shown in comparative example 3 in Table 1 and 12% of LiPF6And (3) salt.
Comparative example 4
LiNi0.5Co0.2Mn0.3O2Artificial graphite battery and packComprises a positive electrode (NCM523 from Union, Congren Lily), a negative electrode (artificial graphite P15 from fir), a diaphragm (PP/PE from Haw), and an electrolyte, wherein the electrolyte is a non-aqueous electrolyte, the total weight of the non-aqueous electrolyte is 100%, and the electrolyte comprises the components with the mass percentage shown in comparative example 4 in Table 1 and 12% of LiPF6And (3) salt.
The performance tests of the examples 1-14 and the comparative examples 1-4 of the invention are carried out, and the test indexes and the test methods are as follows:
(1) the high-temperature cycle performance is shown by testing the capacity retention rate of 1C cycle at 45 ℃ for N times, and the specific method comprises the following steps: the battery after formation was charged to 4.35V (LiNi) at 45 ℃ with 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 200 weeks' cycles was calculated to evaluate the high-temperature cycle performance thereof.
The calculation formula of the capacity retention rate after 200 cycles at 45 ℃ is as follows:
the 200 th cycle capacity retention (%) was (200 th cycle discharge capacity/1 st cycle discharge capacity) × 100%
(2) Method for testing capacity retention rate, capacity recovery rate and thickness expansion rate after 30 days of storage at 60 ℃: charging the formed battery to 4.4V (LiNi) at normal temperature by using a 1C constant current and constant voltage0.5Co0.2Mn0.3O2Artificial graphite), the cutoff current was 0.02C, then 1C constant current discharge to 3.0V, the initial discharge capacity of the battery was measured, then 1C constant current constant voltage charge to 4.4V, the cutoff current was 0.01C, the initial thickness of the battery was measured, then the thickness of the battery was measured after storing the battery at 60 ℃ for 30 days, then 1C constant current discharge to 3.0V, the retention capacity of the battery was measured, then 1C constant current constant voltage charge to 3.0V, the cutoff battery was 0.02C, then 1C constant current discharge to 3.0V, the recovery capacity was measured. The calculation formulas of the capacity retention rate, the capacity recovery rate and the thickness expansion are as follows:
battery capacity retention (%) retention capacity/initial capacity × 100%
Battery capacity recovery (%) -recovery capacity/initial capacity X100%
Battery thickness swelling ratio (%) (thickness after 30 days-initial thickness)/initial thickness × 100%
TABLE 1
The test results of experimental examples 1 to 14 and comparative examples 1 to 4 are shown in table 2 below.
TABLE 2
The results in table 2 show that the addition of the additive for nonaqueous lithium ion battery electrolyte can make the capacity retention rate of the lithium ion battery 73% or more after 200 cycles at 45 ℃, and the capacity retention rate of the lithium ion battery after 30 days of high-temperature storage at 60 ℃ is 72% or more, the capacity recovery rate is 74% or more, and the thick expansion rate is 30% or less. The comparative example, in which such an additive was not added, resulted in a significant decrease in high-temperature capacity retention rate, capacity recovery rate, and cycle performance, and a significant increase in thick expansion rate.
The applicant states that the present invention is described by the above examples of the lithium ion battery nonaqueous electrolyte solution of the present invention and the lithium ion battery comprising the same, but the present invention is not limited to the above examples, that is, the present invention is not meant to be implemented only by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The non-aqueous electrolyte of the lithium ion battery is characterized by comprising a compound additive with the structure shown as the following formula I:
wherein R is nitrile group, nitrile group substituted C1-C4 alkyl.
2. The nonaqueous electrolyte solution for lithium ion batteries according to claim 1, wherein the compound additive is selected from any one of compounds represented by the following structures or a combination of at least two of the compounds:
3. the nonaqueous electrolyte solution for lithium ion batteries according to claim 1 or 2, wherein the compound additive represented by the formula I is contained in an amount of 0.1 to 5% by mass, preferably 1 to 3% by mass, based on 100% by mass of the total mass of the nonaqueous electrolyte solution for lithium ion batteries.
4. The nonaqueous electrolyte solution for a lithium ion battery according to any one of claims 1 to 3, wherein a solvent in the nonaqueous electrolyte solution for a lithium ion battery is selected from any one of ethylene carbonate, propylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, and methylpropyl carbonate, or a combination of at least two thereof.
5. The lithium-ion battery nonaqueous electrolyte solution according to any one of claims 1 to 4, characterized in that the lithium-ion battery nonaqueous electrolyte solution further comprises other additives besides the compound additive represented by formula I;
preferably, the other additive comprises at least one of unsaturated cyclic carbonate ester compounds or sultone compounds;
preferably, the unsaturated cyclic carbonate compound comprises at least one of vinylene carbonate and ethylene carbonate;
preferably, the sultone compound comprises at least one of 1, 3-propane sultone and 1, 4-butane sultone;
preferably, the content of the unsaturated cyclic carbonate compound is 0.1-5% by taking the total mass of the lithium ion battery nonaqueous electrolyte as 100%;
preferably, the content of the sultone compounds in percentage by mass is 0.1-5% based on 100% of the total mass of the lithium ion battery nonaqueous electrolyte.
6. The nonaqueous electrolyte solution for lithium ion batteries according to any one of claims 1 to 5, wherein the other additives further comprise lithium salt additives, and the lithium salt additives comprise LiBOB, LiFSI, LiODFB, LiBF4、LiPO2F2Or a combination of at least two of the foregoing.
7. The nonaqueous electrolyte solution for lithium ion batteries according to any one of claims 1 to 6, wherein the lithium salt-based additive is contained in an amount of 0.1 to 5% by mass based on 100% by mass of the total mass of the nonaqueous electrolyte solution for lithium ion batteries.
8. The nonaqueous electrolyte solution for lithium ion batteries according to any one of claims 1 to 7, wherein the electrolyte in the nonaqueous electrolyte solution for lithium ion batteries is a lithium salt, and the lithium salt is preferably LiPF6；
Preferably, the mass percentage of the electrolyte lithium salt in the lithium ion battery non-aqueous electrolyte is 0.1-20%.
9. A lithium ion battery comprising a positive electrode, a negative electrode, a separator provided between the positive electrode and the negative electrode, and an electrolytic solution, wherein the electrolytic solution is the lithium ion battery nonaqueous electrolytic solution according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode comprises an active material that is LiNixCoyMnzL(1-x-y-z)O2、LiCoxL(1-x')O2、LiNixLyMn(2-x”-y')O4Liz'MPO4At least one of; wherein L is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si and 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 0 and less than or equal to 1, x ' is more than 0.3 and less than or equal to 0.6, y ' is more than 0.01 and less than or equal to 0.2, 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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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020009650A1 (en) * | 1996-12-30 | 2002-01-24 | Christophe Michot | Perfluorinated amide salts and their uses as ionic conducting materials |
| US20080138704A1 (en) * | 2004-05-10 | 2008-06-12 | Nippon Shokubai Co., Ltd. | Material for Electrolytic Solution, Ionic Material-Containing Composition and Use Thereof |
| JP2008251530A (en) * | 2007-03-02 | 2008-10-16 | Nippon Synthetic Chem Ind Co Ltd:The | Electrolyte and lithium secondary battery using the same |
| JP2015191851A (en) * | 2014-03-28 | 2015-11-02 | 株式会社日本触媒 | Nonaqueous electrolyte and power storage device including the same |
| US20150331347A1 (en) * | 2014-05-16 | 2015-11-19 | Canon Kabushiki Kaisha | Electrophotographic member, process cartridge, and electrophotographic apparatus |
| JP2016091906A (en) * | 2014-11-07 | 2016-05-23 | 株式会社日本触媒 | Nonaqueous electrolyte and lithium ion secondary battery arranged by use thereof |
| JP2017010924A (en) * | 2015-06-18 | 2017-01-12 | 株式会社日本触媒 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| CN109326823A (en) * | 2017-07-31 | 2019-02-12 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery non-aqueous electrolyte and lithium-ion battery |
| US20190260080A1 (en) * | 2016-11-24 | 2019-08-22 | Lg Chem, Ltd. | Non-aqueous Electrolyte and Lithium Secondary Battery Including the Same |
-
2020
- 2020-07-24 CN CN202010728485.1A patent/CN111883836A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020009650A1 (en) * | 1996-12-30 | 2002-01-24 | Christophe Michot | Perfluorinated amide salts and their uses as ionic conducting materials |
| US20080138704A1 (en) * | 2004-05-10 | 2008-06-12 | Nippon Shokubai Co., Ltd. | Material for Electrolytic Solution, Ionic Material-Containing Composition and Use Thereof |
| JP2008251530A (en) * | 2007-03-02 | 2008-10-16 | Nippon Synthetic Chem Ind Co Ltd:The | Electrolyte and lithium secondary battery using the same |
| JP2015191851A (en) * | 2014-03-28 | 2015-11-02 | 株式会社日本触媒 | Nonaqueous electrolyte and power storage device including the same |
| US20150331347A1 (en) * | 2014-05-16 | 2015-11-19 | Canon Kabushiki Kaisha | Electrophotographic member, process cartridge, and electrophotographic apparatus |
| JP2016091906A (en) * | 2014-11-07 | 2016-05-23 | 株式会社日本触媒 | Nonaqueous electrolyte and lithium ion secondary battery arranged by use thereof |
| JP2017010924A (en) * | 2015-06-18 | 2017-01-12 | 株式会社日本触媒 | Nonaqueous electrolyte and nonaqueous electrolyte secondary battery using the same |
| US20190260080A1 (en) * | 2016-11-24 | 2019-08-22 | Lg Chem, Ltd. | Non-aqueous Electrolyte and Lithium Secondary Battery Including the Same |
| CN109326823A (en) * | 2017-07-31 | 2019-02-12 | 深圳新宙邦科技股份有限公司 | Lithium-ion battery non-aqueous electrolyte and lithium-ion battery |
Non-Patent Citations (1)
| Title |
|---|
| JOHAN SCHEERS: "Novel lithium imides; effects of -F, -CF3, and -C≡N substituents on lithium battery salt stability and dissociation", 《THE ELECTROCHEMICAL SOCIETY OF JAPAN》 * |
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