CN116646603A - Lithium ion battery nonaqueous electrolyte additive capable of reducing internal resistance of battery and application thereof - Google Patents
Lithium ion battery nonaqueous electrolyte additive capable of reducing internal resistance of battery and application thereof Download PDFInfo
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- CN116646603A CN116646603A CN202310850412.3A CN202310850412A CN116646603A CN 116646603 A CN116646603 A CN 116646603A CN 202310850412 A CN202310850412 A CN 202310850412A CN 116646603 A CN116646603 A CN 116646603A
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- Prior art keywords
- lithium ion
- ion battery
- nonaqueous electrolyte
- lithium
- electrolyte
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Links
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 67
- 239000000654 additive Substances 0.000 title claims abstract description 56
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 47
- 230000000996 additive effect Effects 0.000 title claims abstract description 36
- 239000003792 electrolyte Substances 0.000 claims abstract description 62
- XSUMSESCSPMNPN-UHFFFAOYSA-N propane-1-sulfonate;pyridin-1-ium Chemical compound C1=CC=NC=C1.CCCS(O)(=O)=O XSUMSESCSPMNPN-UHFFFAOYSA-N 0.000 claims abstract description 19
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims description 32
- 229910003002 lithium salt Inorganic materials 0.000 claims description 28
- 159000000002 lithium salts Chemical class 0.000 claims description 28
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 14
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical group 0.000 claims description 3
- 125000002355 alkine group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 2
- GWAOOGWHPITOEY-UHFFFAOYSA-N 1,5,2,4-dioxadithiane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCO1 GWAOOGWHPITOEY-UHFFFAOYSA-N 0.000 claims description 2
- RYIRMSRYCSMGJA-UHFFFAOYSA-N 1,5,2,4-dioxadithiepane 2,2,4,4-tetraoxide Chemical compound O=S1(=O)CS(=O)(=O)OCCO1 RYIRMSRYCSMGJA-UHFFFAOYSA-N 0.000 claims description 2
- 229910013553 LiNO Inorganic materials 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 229910013188 LiBOB Inorganic materials 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000007600 charging Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000002000 Electrolyte additive Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000010439 graphite Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 16
- -1 pyridine cations Chemical class 0.000 description 16
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 15
- LXSLZSJZGMWGOL-UHFFFAOYSA-N butane-1-sulfonate;pyridin-1-ium Chemical compound C1=CC=[NH+]C=C1.CCCCS([O-])(=O)=O LXSLZSJZGMWGOL-UHFFFAOYSA-N 0.000 description 11
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical group O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 10
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 10
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 229910021382 natural graphite Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- JFLRBGOBOJWPHI-UHFFFAOYSA-N pyridin-1-ium-1-sulfonate Chemical compound [O-]S(=O)(=O)[N+]1=CC=CC=C1 JFLRBGOBOJWPHI-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- H01M10/05—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
-
- 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 application discloses a lithium ion battery nonaqueous electrolyte additive capable of reducing internal resistance of a battery, and a lithium ion battery nonaqueous electrolyte containing the additive and application thereof, and belongs to the technical field of lithium ion batteries. The additive is at least one of Pyridinium Propane Sulfonate (PPS) or a derivative thereof. The lithium ion battery electrolyte additive can generate electrostatic action with the negative electrode in the battery charging process to be adsorbed on the surface of the negative electrode, form a compact SEI film, play a role in protecting the negative electrode and the electrolyte, and the SEI film is stable, compact and low in impedance, and can improve the cycle stability, low-temperature performance and rate capability of the battery.
Description
Technical Field
The application belongs to the technical field of lithium ion batteries, and particularly relates to a lithium ion battery nonaqueous electrolyte additive capable of reducing internal resistance of a battery, a lithium ion battery nonaqueous electrolyte containing the additive and application of the lithium ion battery nonaqueous electrolyte additive.
Background
The lithium ion battery has the advantages of high specific energy, low cost, high stability, long service life and the like. Has wide application in the fields of electric automobiles, 3C numbers and the like. The rapid development of new energy industry has higher and higher performance requirements for lithium ion batteries.
The solid electrolyte interface film (SEI film) is usually formed at the interface between the negative electrode and the electrolyte of the lithium ion battery, and the SEI film can prevent the co-intercalation of solvents and the decomposition of the electrolyte, so that the cycle performance and the service life of the battery are improved. However, in the process of operating the ion battery, the SEI film is also continuously destroyed and reconstructed due to the volume change of the negative electrode in the process of removing lithium ions, and electrolyte and active lithium are consumed, so that the capacity of the battery is attenuated. In addition, too thin an SEI film may result in insufficient protection of the electrode, reduced cycle life, and too thick an SEI film may result in increased internal resistance, reduced low temperature performance, rate capability and energy density of the battery. Thus, a stable, thin and dense SEI film may improve the stability of a battery during cycling or in extreme environments (high temperature, low temperature or high power). By adding a film forming additive into the electrolyte, the stability of the SEI film is improved, the internal resistance of the SEI film is reduced, and the SEI film is an important means for improving the cycle, low temperature and high power performance of the battery.
The present application has been made for the above reasons.
Disclosure of Invention
The film forming additive has various kinds and functions, and the existing inner salt type additive is used for the low-temperature performance and the multiplying power performance of the lithium ion battery, and because the inner salt type additive contains pyridine cations, the inner salt type additive is adsorbed on the surface of a negative electrode under the action of an electronic effect, a stable and low-impedance SEI film is formed, and the low-temperature performance and the multiplying power performance of the battery are obviously improved.
For the above reasons, in view of the problems or drawbacks of the prior art, the present application aims to provide a nonaqueous lithium ion battery electrolyte additive capable of reducing internal resistance of a battery, and a nonaqueous lithium ion battery electrolyte and application containing the same, which solve or at least partially solve the above technical drawbacks of the prior art.
In order to achieve the first object of the present application, the present application adopts the following technical scheme:
a lithium ion battery nonaqueous electrolyte additive capable of reducing internal resistance of a battery, wherein the additive is at least one of Pyridinium Propane Sulfonate (PPS) or derivatives thereof, and the structural formula of the additive is shown as follows:
wherein n=0, 1, 2, 3, 4, 5 or 6; r is R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 And is selected from any one of hydrogen atom, fluorine atom, alkyl group, olefin group, alkyne group, alkoxy group and aromatic group.
The following are to be described:
the additive of the application is derived from pyridinium propane sulfonate, comprises pyridinium cations, sulfonate anions, other carbon skeletons, hydrogen atoms, fluorine atoms, alkyl groups, olefin groups, alkyne groups, alkoxy groups or aromatic groups which can be converted, and is a derivative of the pyridinium sulfonate.
A second object of the present application is to provide the use of the above additive for preparing a non-aqueous electrolyte for a lithium ion battery.
A lithium ion battery nonaqueous electrolyte comprising an electrolyte lithium salt, an organic solvent, a Pyridinium Propane Sulfonate (PPS) or a derivative thereof as described above.
Further, according to the technical scheme, the non-aqueous electrolyte of the lithium ion battery can further comprise an auxiliary agent and/or other additives.
Further, according to the above technical scheme, the electrolyte lithium salt includes lithium hexafluorophosphate (LiPF 6 ) Lithium perchlorate (LiClO) 4 ) Lithium tetrafluoroborate (LiBF) 4 ) One or more of lithium bis (oxalato) borate (LiBOB), lithium bis (oxalato) borate (LiDFOB), lithium triflate (LiOTF), lithium bis (fluorosulfonyl) imide (LiLSI) or lithium bis (trifluoromethylsulfonyl) imide (LITFSI).
Further, according to the technical scheme, the molar concentration of the electrolyte lithium salt in the nonaqueous electrolyte of the lithium ion battery is 0.5-3mol/L.
Further, according to the technical scheme, the organic solvent is at least one of Ethylene Carbonate (EC), propylene Carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), fluorocarbonate solvent, ethyl Acetate (EA), propyl Acetate (PA), methyl Propionate (MP), ethyl Propionate (EP) and Propyl Propionate (PP).
Further, according to the technical scheme, the Pyridinium Propane Sulfonate (PPS) or the derivative thereof accounts for 0.01% -10% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
Preferably, the auxiliary agent or additive comprises ethylene carbonate (VC), ethylene carbonate (VEC), ethylene sulfate (DTD), ethylene methane disulfonate (MMDS), 1, 3-propyl sultone (1,3PS), ethylene Sulfite (ES), fluoroethylene carbonate (FEC), lithium nitrate (LiNO) 3 ) Lithium difluorophosphate (LiPO) 2 F 2 ) One or more of lithium oxalato borate (LiBOB), lithium difluorooxalato borate (LiDFOB), adiponitrile (AND) AND Succinonitrile (SN).
Preferably, according to the technical scheme, the mass of the other additives accounts for 0.01% -10% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
A third object of the present application is to provide an application of the above-mentioned nonaqueous electrolyte for lithium ion batteries in lithium ion batteries. The lithium ion battery using the non-aqueous electrolyte can reduce internal resistance, improve stability and improve low-temperature performance and rate performance.
The lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode and a non-aqueous electrolyte, wherein the non-aqueous electrolyte is the non-aqueous electrolyte of the lithium ion battery.
As a preferable technical scheme of the application, the lithium ion battery comprises a lithium iron phosphate// graphite battery, a graphite// lithium metal battery, a lithium cobaltate// graphite battery, a lithium cobaltate// lithium metal battery, a ternary nickel cobalt manganese// graphite battery and the like.
Compared with the prior art, the application has the following beneficial effects:
(1) The lithium ion battery electrolyte additive can generate electrostatic action with the negative electrode in the battery charging process to be adsorbed on the surface of the negative electrode, form a compact SEI film, play a role in protecting the negative electrode and the electrolyte, and the SEI film is stable, compact and low in impedance, and can improve the cycle stability, low-temperature performance and rate capability of the battery.
(2) The non-aqueous electrolyte additive for the lithium ion battery is not only suitable for the field of lithium ion batteries, but also suitable for the field of sodium ion batteries, and can improve the stability, low-temperature performance and rate capability of the sodium ion battery.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are only some embodiments of the application, and that other drawings can be obtained according to these drawings without inventive effort to a person skilled in the art.
Fig. 1 the first cycle charge and discharge curves of graphite// lithium metal half-cells prepared in example 1 and comparative example 1.
Detailed Description
The application is described in further detail below by way of examples.
For a better understanding of the present application, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Accordingly, unless specifically indicated otherwise, the numerical parameters set forth in the specification are approximations that may vary depending upon the desired properties sought to be obtained. Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The equipment and materials used in the present application are commercially available or are commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
The electrolyte in the following examples was prepared by mixing an organic solvent and an auxiliary agent in a certain proportion in a glove box in an argon atmosphere (moisture < 1ppm, oxygen content < 1 ppm), and adding an electrolyte lithium salt and an additive.
The electrolytes obtained in example 1 and comparative example 1 were assembled into a natural graphite// lithium metal button cell, and the separator was a glass fiber separator. The preparation method comprises the following steps:
1) Manufacturing a graphite negative electrode: and (3) fully stirring and uniformly mixing a graphite anode material (Gr), a conductive Super P and a binder sodium carboxymethylcellulose (CMC) in a deionized water solvent according to a mass ratio of 90:5:5, coating the mixture on a copper foil, and drying and cutting the mixture to obtain an anode piece (a wafer with the diameter of 12 mm).
2) The CR-2032 coin cell was assembled in a glove box.
The nonaqueous electrolytic solutions obtained in examples 2 to 7 and comparative example 2 were assembled into a flexible battery of 1.6Ah, the positive electrode was lithium iron phosphate, the negative electrode was graphite, and the separator was a polyolefin separator.
The respective performance test methods involved in the following examples or comparative examples are specifically as follows:
the ohmic internal resistance testing method comprises the following steps: (1) the battery to be tested was charged to 3.65V at a current of 0.2C (1c=1600 mA) and charged to a current of less than 0.05C at a constant voltage of 3.65V. (2) Applying alternating voltage to the battery, measuring the impedance of the battery, and calculating the internal resistance of the battery according to the impedance of the battery and the phase difference.
-20 ℃ low temperature performance test method: (1) after the battery to be tested is stood at 25 ℃ for 8 hours, the battery to be tested is charged to 3.65V at a current of 0.2C, then is charged to a current of less than 0.05C at a constant voltage of 3.65V, and then is discharged to 2.5V at a constant voltage of 0.2C. (2) The above steps are repeated twice, and then the constant voltage charge is carried out until the current is less than 0.05C after the charge is carried out to 3.65V. (3) Then, the mixture was allowed to stand at-20℃for 8 hours, and discharged to 2V at a current of 0.1 ℃. The discharge capacities at 25℃and-20℃were recorded, and the low-temperature discharge capacity/normal-temperature discharge capacity ratio (capacity retention) was calculated.
And (3) multiplying power performance test: (1) after standing for 8h at 25 ℃, charging to 3.65V at a current of 0.1C, then charging to a current of less than 0.05C at a constant voltage of 3.65V, and discharging to 2.5V at 0.1C, the steps are circulated twice. (2) Constant current charging to 3.65V at 25 ℃ with 0.1C current, followed by constant voltage charging to current less than 0.05C at 3.65V, followed by constant current discharging to 2.5V with 3C current. (3) The discharge capacity ratio at 3C/0.1C current was calculated.
Example 1
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: pyridinium propane sulfonate.
The non-aqueous electrolyte of the lithium ion battery consists of lithium salt, an organic solvent and pyridinium propane sulfonate; the concentration of lithium salt in the electrolyte is 1.0mol/L, and the lithium salt is lithium hexafluorophosphate; the organic solvent is propylene carbonate; the pyridinium propane sulfonate accounts for 1% of the total mass of the electrolyte; no other additives.
The electrolyte obtained in this example was used to assemble a CR-2032 button cell in a glove box, the active material was natural graphite, and the counter electrode was lithium metal.
Example 2
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: pyridinium propane sulfonate.
The non-aqueous electrolyte of the lithium ion battery of the embodiment consists of lithium salt, organic solvent, pyridinium propane sulfonate and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the pyridinium propane sulfonate accounts for 1% of the total mass of the electrolyte; the other additive is vinylene carbonate, and the vinylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this example was assembled into lithium iron phosphate// graphite pouch cells.
Example 3
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: pyridinium propane sulfonate.
The non-aqueous electrolyte of the lithium ion battery of the embodiment consists of lithium salt, organic solvent, pyridinium propane sulfonate and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the pyridinium propane sulfonate accounts for 3% of the total mass of the electrolyte, the other additives are vinylene carbonate, and the vinylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this example was assembled into lithium iron phosphate// graphite pouch cells.
Example 4
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: butanesulfonic acid pyridinium salt (BPS).
The lithium ion battery electrolyte of the embodiment consists of lithium salt, an organic solvent, butane sulfonic acid pyridinium salt and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the other additive of 1% of the total mass of the electrolyte is vinylene carbonate, and the vinylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this example was assembled into lithium iron phosphate// graphite pouch cells.
Example 5
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: butanesulfonic acid pyridinium salt (BPS).
The lithium ion battery electrolyte of the embodiment consists of lithium salt, an organic solvent, butane sulfonic acid pyridinium salt and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the pyridinium butane sulfonate accounts for 3% of the total mass of the electrolyte, the other additives are vinylene carbonate, and the vinylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this example was assembled into lithium iron phosphate// graphite pouch cells.
Example 6
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: butanesulfonic acid pyridinium salt (BPS).
The lithium ion battery electrolyte of the embodiment consists of lithium salt, an organic solvent, butane sulfonic acid pyridinium salt and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the pyridinium butane sulfonate accounts for 1% of the total mass of the electrolyte, the other additives are fluoroethylene carbonate, and the fluoroethylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this example was assembled into lithium iron phosphate// graphite pouch cells.
Example 7
The lithium ion battery nonaqueous electrolyte additive capable of reducing the internal resistance of the battery in the embodiment specifically comprises the following components: butanesulfonic acid pyridinium salt (BPS).
The lithium ion battery electrolyte of the embodiment consists of lithium salt, an organic solvent, butane sulfonic acid pyridinium salt and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the pyridinium butane sulfonate accounts for 3% of the total mass of the electrolyte, the other additives are fluoroethylene carbonate, and the fluoroethylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this example was assembled into lithium iron phosphate// graphite pouch cells.
Comparative example 1
The lithium ion battery electrolyte of the comparative example consists of lithium salt and an organic solvent; the concentration of lithium salt in the electrolyte is 1.0mol/L, and the lithium salt is lithium hexafluorophosphate; the organic solvent is propylene carbonate.
The electrolyte obtained in this comparative example was assembled into a CR-2032 button cell in a glove box, the active material was natural graphite, and the counter electrode was lithium metal.
Comparative example 2
The lithium ion battery electrolyte of the comparative example consists of lithium salt, an organic solvent and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the other additive is vinylene carbonate, and the vinylene carbonate accounts for 3% of the total mass of the electrolyte.
The electrolyte prepared in this comparative example was assembled into lithium iron phosphate// graphite pouch cells.
Comparative example 3
The lithium ion battery electrolyte of the comparative example consists of lithium salt, an organic solvent and other additives; the lithium salt in the electrolyte is lithium hexafluorophosphate, and the concentration is 1.0mol/L; the organic solvent is a mixed solvent of ethylene carbonate, propylene carbonate and methyl ethyl carbonate, and the mass ratio of the organic solvent to the mixed solvent is 33:5:62; the other additives are fluoroethylene carbonate, and the fluoroethylene carbonate accounts for 3 percent of the total mass of the electrolyte.
The electrolyte prepared in this comparative example was assembled into lithium iron phosphate// graphite pouch cells.
Performance test:
the properties of the graphite half-cells prepared in example 1 and comparative example 1 are shown in fig. 1.
The incompatibility of propylene carbonate based electrolytes with graphite is common in the industry, so it is effective to examine the film forming properties and compatibility of additives on the surface of graphite with propylene carbonate based electrolytes. As can be seen from fig. 1, the addition of PPS can make the propylene carbonate-based electrolyte compatible with graphite, indicating that PPS can effectively form a film on the graphite surface, preventing electrolyte decomposition and solvent co-intercalation.
Table 1 shows the results of ohmic resistance tests for the soft pack batteries of examples 2 to 7 and comparative examples 2 to 3
As can be seen from the data in table 1, after the pyridinium propane sulfonate or its derivative is added as an additive to the electrolyte, a low-resistance SEI film is formed by the adsorption of the pyridinium propane sulfonate or its derivative on the negative electrode, so that the internal resistance of the battery can be reduced, and the low-temperature performance and the rate performance of the battery can be improved. The low-temperature performance can be improved by more than 15% compared with the comparative example, and the 3C rate performance can be improved by more than 25%.
It should be noted that the foregoing embodiments are merely specific examples of the present application, which are described in more detail and are not to be construed as limiting the scope of the application. It should be noted that modifications and improvements can be made by those skilled in the art without departing from the spirit of the application, and these alternatives fall within the scope of the application.
Claims (10)
1. A lithium ion battery nonaqueous electrolyte additive capable of reducing internal resistance of a battery is characterized in that: the additive is at least one of Pyridinium Propane Sulfonate (PPS) or a derivative thereof, and the structural formula of the additive is shown as follows:
wherein n=0, 1, 2, 3, 4, 5 or 6; r is R 1 、R 2 、R 3 、R 4 、R 5 And R is 6 And is selected from any one of hydrogen atom, fluorine atom, alkyl group, olefin group, alkyne group, alkoxy group and aromatic group.
2. The use of the lithium ion battery nonaqueous electrolyte additive of claim 1 in the preparation of a lithium ion battery nonaqueous electrolyte.
3. A lithium ion battery nonaqueous electrolyte, characterized in that: comprising an electrolyte lithium salt, an organic solvent, pyridinium Propane Sulfonate (PPS) or a derivative thereof according to claim 1.
4. The lithium ion battery nonaqueous electrolyte according to claim 3, wherein: the lithium ion battery nonaqueous electrolyte also comprises an auxiliary agent and/or other additives.
5. The lithium ion battery nonaqueous electrolyte according to claim 3, wherein: the molar concentration of the electrolyte lithium salt in the nonaqueous electrolyte of the lithium ion battery is 0.5-3mol/L.
6. The lithium ion battery nonaqueous electrolyte according to claim 3, wherein: the Pyridinium Propane Sulfonate (PPS) or the derivative thereof accounts for 0.01-10% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
7. The lithium ion battery nonaqueous electrolyte according to claim 4, wherein: the other additives include ethylene carbonate (VC), ethylene carbonate (VEC), ethylene sulfate (DTD), ethylene methane disulfonate (MMDS), 1, 3-propylsultone (1,3PS), ethylene Sulfite (ES), fluoroethylene carbonate (FEC), lithium nitrate (LiNO) 3 ) Lithium difluorophosphate (LiPO) 2 F 2 ) Boric acid di (oxalic acid)One or two or more of Lithium (LiBOB), lithium difluorooxalato borate (LiDFOB), adiponitrile (AND) AND Succinonitrile (SN).
8. The lithium ion battery nonaqueous electrolyte according to claim 4, wherein: the mass of the other additives accounts for 0.01% -10% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
9. Use of the non-aqueous electrolyte of a lithium ion battery according to any one of claims 3-8 in a lithium ion battery.
10. A lithium ion battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a nonaqueous electrolyte, the nonaqueous electrolyte being the lithium ion battery nonaqueous electrolyte according to any one of claims 3 to 8.
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