CN103000942A - Additive promoting graphite cathode to generate solid electrolyte interfacial film, and application thereof - Google Patents
Additive promoting graphite cathode to generate solid electrolyte interfacial film, and application thereof Download PDFInfo
- Publication number
- CN103000942A CN103000942A CN2011102726211A CN201110272621A CN103000942A CN 103000942 A CN103000942 A CN 103000942A CN 2011102726211 A CN2011102726211 A CN 2011102726211A CN 201110272621 A CN201110272621 A CN 201110272621A CN 103000942 A CN103000942 A CN 103000942A
- Authority
- CN
- China
- Prior art keywords
- additive
- electrolyte
- carbon
- carbonate
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000654 additive Substances 0.000 title claims abstract description 54
- 230000000996 additive effect Effects 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000010439 graphite Substances 0.000 title claims abstract description 28
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 28
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 9
- 230000001737 promoting effect Effects 0.000 title abstract 2
- 239000003792 electrolyte Substances 0.000 claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000002883 imidazolyl group Chemical group 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 14
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 13
- -1 aldehyde radical Chemical class 0.000 claims description 10
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 2
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000002466 imines Chemical class 0.000 claims description 2
- 125000000468 ketone group Chemical group 0.000 claims description 2
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 claims description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical group C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract 3
- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 description 1
- XLXCHZCQTCBUOX-UHFFFAOYSA-N 1-prop-2-enylimidazole Chemical compound C=CCN1C=CN=C1 XLXCHZCQTCBUOX-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- MOEGVLVTWRNNKL-UHFFFAOYSA-N 2-(benzenesulfonyl)-5-methyl-1H-imidazole Chemical class CC=1N=C(NC1)S(=O)(=O)C1=CC=CC=C1 MOEGVLVTWRNNKL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910000552 LiCF3SO3 Inorganic materials 0.000 description 1
- VIHYIVKEECZGOU-UHFFFAOYSA-N N-acetylimidazole Chemical compound CC(=O)N1C=CN=C1 VIHYIVKEECZGOU-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The invention provides an additive used for promoting a graphite cathode to generate a solid electrolyte interfacial film. The additive is characterized in that the additive has a structural formula below. The structure is a nitrogen-site unitary substitution on an imidazole ring (X). The invention also provides a propylene carbonate electrolyte containing the additive, and an application of the additive-containing propylene carbonate electrolyte in lithium ion batteries. The melting point of the electrolyte system is greatly reduced, such that lithium ion batteries employing the additive-containing propylene carbonate electrolyte has good low-temperature performance.
Description
Technical field
The present invention relates to a kind of additive and application, specifically relate to a kind of graphite cathode material that promotes and in cyclic process, generate the electrolysis additive of solid electrolyte interface film, and the application in lithium ion battery.The invention belongs to electrochemical field.
Background technology
Lithium ion battery is as a kind of energy density is high, output voltage is high, memory-less effect, eco-friendly Green Chemistry power supply, have good economic benefit, social benefit and strategic importance, be widely used in the every field such as mobile communication, digital product.
At present the electrolyte solvent that uses of lithium ion battery almost all is to add some linear carbonate with ethylene carbonate (EC) as key component, the solvent mixture that forms such as dimethyl carbonate (DMC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) etc.The sharpest edges of ethylene carbonate are and can form form compact and stable solid electrolyte interface film (SEI film) at high-graphitized carbon material surface, because formed passivating film is comparatively fine and close, can effectively prevent further decomposition and the altogether embedding of ethylene carbonate, thereby guarantee the normal chemical property of carbon negative pole material.But the fusing point of EC higher (about 36oC) itself, although can reduce by adding the cosolvent such as DEC, DMC the fusing point of electrolyte, but its minimum serviceability temperature also only is-20oC usually, and this has limited the performance of lithium ion battery under cryogenic conditions significantly.Present fast development along with high-technology fields such as military affairs, polar region scientific investigation and Aero-Space, the low temperature scope of application and performance to lithium ion battery have proposed very high requirement, therefore the cryogenic property of lithium ion battery is one of pressing issues that must solve, and the chief component of electrolyte is especially important to the expansion of performance of lithium ion battery.Wherein the electrolyte take propene carbonate (PC) as solvent is that a kind of feasible approach that provides is provided.
The fusing point of propene carbonate is more much lower than EC, is about-49oC, has good cryogenic property, and its conductivity is higher, and price is also cheap, therefore is considered to only solvent for low-temperature electrolyte.But the compatibility of the electrolyte take propene carbonate as the primary solvent component and high-graphitized carbon electrode material is poor, efficiency for charge-discharge is low, its main cause is that propene carbonate decomposes on the surface of graphite electrode, can not form densification, effective SEI film, present corresponding to the platform about the 0.7-0.8V (with respect to Li/Li+) of the common embedding of solvation Li+ at discharge curve, finally cause peeling off of graphite electrode, efflorescence occurs, cause completely losing of the obvious decline of graphite electrode reversible capacity or even cycle performance, therefore it is generally acknowledged that propene carbonate electrolyte is not suitable in the lithium ion battery of graphitized material as negative pole.
Film for additive is that it preferentially reduces on the negative materials such as graphite surface, forms a class electrolysis additive of SEI film.By in propylene carbonate ester group electrolyte, adding film for additive, can make graphitized carbon material in propylene carbonate ester group electrolyte, have good chemical property, improve the lithium ion battery cryogenic property thereby play, the effect of the expansion lithium ion battery scope of application.At present, the film for additive that uses of research mainly contains: with CO2, SO2 as the gas of representative, reach with the liquid additive as representative such as vinylene carbonate (VC), benzimidazole, ethylene sulfite, cyano group furans as the solid of representative with LiCO3.But there are the low problem of solubility in solid and additives gas, have therefore limited the performance of its effect.Liquid additive is the problem of existence and stability and toxicity aspect often then, and these problems have limited graphite electrode in the PC base electrolyte, thereby have finally limited the application of lithium ion battery under cryogenic conditions.
Summary of the invention
An object of the present invention is to provide a kind of graphite cathode that promotes and generate the additive of SEI film in PC base electrolyte, another object of the present invention provides the lithium ion battery that a kind of employing contains the electrolyte assembling of this additive.
The invention provides a kind of graphite cathode that promotes and generate the additive of solid electrolyte interface film, it is characterized in that: described additive is following structural formula,
The said structure formula is that the monobasic of nitrogen position on the imidazole ring replaces (X), wherein X must be the functional group of containing unsaturated bond, particularly, X be carbon number between 2-10, contain thiazolinyl, alkenylene, alkynyl, aldehyde radical, ester group, ketone group, cyano group, azo-compound, phenyl and the phenyl substituted thing of the two keys of carbon-to-carbon double bond, carbon-to-carbon triple bond, carbon-oxygen, carbon-nitrogen triple bond, the two keys of nitrogen-nitrogen; Additive is to have a kind of of above structural formula or its combination; The mass fraction of additive in propylene carbonate ester group electrolyte is 0.5%-10%.
The described propylene carbonate ester group electrolyte that contains additive refers to take propene carbonate as electrolyte system unique or that primary solvent forms, namely can be with the electrolyte of pure propene carbonate as solvent, also can be binary or the multiple mixed solvent of propene carbonate and ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate ester solvent, wherein the mass fraction of propene carbonate in solvent be 50%-99.5%.
The described used electrolytic salt of propylene carbonate ester group electrolyte that contains additive is electrolytic salt commonly used in the present commercialization electrolyte system, is lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), di-oxalate lithium borate (LiBC
4O
8, LiBOB), LiBF4 (LiBF
4), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), tetraethyl ammonium tetrafluoroborate ((C
2H
5)
4NBF
4), two (trifluoromethane sulfonic acid acyl) imine lithium (LiN (CF
3SO
2)
2), methyltriethylammonitetrafluoroborate tetrafluoroborate (CH
3(C
2H
5)
3NBF
4) in a kind of or its combination.
The invention provides a kind of propylene carbonate ester group electrolyte that contains additive.
The invention provides a kind of application of propylene carbonate ester group electrolyte in lithium ion battery that contains additive.
The invention provides the lithium ion battery that a kind of employing contains the propylene carbonate ester group electrolyte assembling of additive, because the adding of additive can make graphite form the SEI film in PC base electrolyte, and PC is the main or unique composition in the electrolyte solvent, the fusing point decrease of electrolyte system, thereby adopt this lithium ion battery that contains the PC base electrolyte assembling of additive to have preferably cryogenic property.
Description of drawings
Fig. 1 is the cycle performance curve of graphite electrode in the electrolyte that adopts embodiment 1, Comparative Examples 1, Comparative Examples 2 gained.
Stereoscan photograph after Fig. 2 circulation that is graphite electrode in adopting the PC base electrolyte of embodiment 1 gained 20 times.
FT-IR spectrogram after Fig. 3 circulation that is graphite electrode in adopting the PC base electrolyte of embodiment 1 gained 20 times.
Embodiment
The below will be described in more detail by embodiment, but protection scope of the present invention is not limited to these embodiment.
Preparation PC and DMC mass ratio are that 1: 1 LiPF6 concentration is the PC base electrolyte 500ml of 1mol/L in glove box, and mixing leaves standstill.Add 0.5 gram 1-vinyl imidazole (structural formula is as follows, and X is vinyl) in 9.5 this kind of gram electrolyte, mixing leaves standstill.Obtain containing the PC base electrolyte of additive, the content of additive is 5wt%.
The preparation of graphite electrode: after a certain amount of MCMB graphite cathode material (CMS), conductive agent acetylene black and binding agent Kynoar (PVDF) be ground according to a certain percentage, add a certain amount of 1-METHYLPYRROLIDONE (NMP), obtain uniform slurry, be coated on the Copper Foil and under the 120oC vacuum condition, dried by the fire 12 hours, obtain cathode pole piece after rolling.
Cycle performance of lithium ion battery test: adopt the cylindrical simulated battery of stainless steel, with graphite electrode as Electrode, with lithium metal as to electrode, take the basic electrolyte of the PC that contains additive that makes as electrolyte, with Celgard 2325 perforated membranes as barrier film, with battery mould, after the barrier film drying, in glove box, be assembled into simulated battery.The voltage range that discharges and recharges is 0.001-2V (with respect to Li/Li+), and charge-discharge velocity is 0.2C.Gained cycle performance curve is shown in Fig. 1 (▲).Discharge capacity is 208.2mAh/g first, and after 20 circulations, discharge capacity is 194.6mAh/g, and capability retention is 93.5%.Illustrate that graphite electrode has preferably cycle performance in containing the PC base electrolyte of additive.
Microscopic appearance and FT-IR test: in glove box, take simulated battery apart, 20 times graphite cathode material of circulation is stripped down from Copper Foil, with the DMC eluent solvent of LITHIUM BATTERY several times, after under vacuum condition, DMC being volatilized fully, put into rapidly respectively that scanning electron microscope example chamber and infrared spectrometer carry out the microscopic appearance test and FT-IR tests.Spherical CMS surface is covered by the skin covering of the surface of one deck densification as can see from Figure 2, this one deck skin covering of the surface is the SEI film that is formed at the CMS Surface disintegration by additive, it can effectively suppress decomposition and the common embedding of PC solvent molecule, makes graphite material have normal chemical property in PC base electrolyte.FT-IR test result (Fig. 3) then belongs to the infrared absorption peak of lithium alkylide and lithium carbonate in the SEI film of additives decompose formation, has confirmed the formation of graphite electrode surface SEI.
Embodiment 2
Preparation LiPF6 concentration is the pure PC electrolyte 500ml of 1mol/L in glove box, and mixing leaves standstill.Add 1 gram 1-vinyl imidazole in 9 this kind of gram electrolyte, mixing leaves standstill.Obtain containing the PC base electrolyte of additive, the content of additive is 10wt%.
Embodiment 3
The LiBF4 concentration of preparing PC, DMC, DEC mass ratio be in glove box 2: 1: 1 is the PC base electrolyte 500ml of 1mol/L, and mixing leaves standstill.Add 0.2 gram N-allyl imidazole (structural formula is as follows, and X is pi-allyl) in 9.8 this kind of gram electrolyte, mixing leaves standstill.Obtain containing the PC base electrolyte of additive, the content of additive is 2wt%.
Embodiment 4
LiN (CF3SO2) 2 concentration of preparing PC, DMC, DEC mass ratio be in glove box 4: 1: 1 are the PC base electrolyte 500ml of 1mol/L, and mixing leaves standstill.Add 0.4 gram 1-to Methyl benzenesulfonyl imidazoles (structural formula such as figure below, X are to Methyl benzenesulfonyl) in 9.6 this kind of gram electrolyte, mixing leaves standstill.Obtain containing the PC base electrolyte of additive, the content of additive is 4wt%.
Preparation PC and EC mass ratio are that 2: 1 LiCF3SO3 concentration is the PC base electrolyte 500ml of 1mol/L in glove box, and mixing leaves standstill.Add 0.5 gram 1-acetyl imidazole (structural formula such as figure below, X are acetyl group) in 9.5 this kind of gram electrolyte, mixing leaves standstill.Obtain containing the PC base electrolyte of additive, the content of additive is 5wt%.
Comparative Examples
LiPF6 take the pure PC of 1mol/L as solvent studies the cycle performance of CMS graphite electrode as electrolyte.The preparation of graphite electrode and the test of cycle performance of lithium ion battery such as embodiment 1.The cycle performance curve is such as Fig. 1 (●) shown in, because PC electrolyte is decomposing on the surface of graphite electrode in the discharge process first, can not form densification, effective SEI film, the constantly altogether embedding of solvation Li+ occurs, finally cause peeling off of graphite electrode, efflorescence occurs, thereby can not discharge and recharge normally by graphite electrode, its follow-up discharge capacity is almost 0.
Claims (5)
1. the invention provides a kind of graphite cathode that promotes and generate the additive of solid electrolyte interface film, it is characterized in that: described additive is following structural formula,
The said structure formula is that the monobasic of nitrogen position on the imidazole ring replaces (X), wherein X must be the functional group of containing unsaturated bond, particularly, X be carbon number between 2-10, contain thiazolinyl, alkenylene, alkynyl, aldehyde radical, ester group, ketone group, cyano group, azo-compound, phenyl and the phenyl substituted thing of the two keys of carbon-to-carbon double bond, carbon-to-carbon triple bond, carbon-oxygen, carbon-nitrogen triple bond, the two keys of nitrogen-nitrogen; Additive is to have a kind of of above structural formula or its combination; The mass fraction of additive in propylene carbonate ester group electrolyte is 0.5%-10%.
2. described promotion graphite cathode generates the additive of solid electrolyte interface film according to claim 1, it is characterized in that: the described propylene carbonate ester group electrolyte that contains additive refers to take propene carbonate as electrolyte system unique or that primary solvent forms, namely can be with the electrolyte of pure propene carbonate as solvent, also can be binary or the multiple mixed solvent of propene carbonate and ethylene carbonate, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate ester solvent, wherein the mass fraction of propene carbonate in solvent be 50%-99.5%.
3. described graphite cathode generates the additive of solid electrolyte interface film according to claim 1, it is characterized in that: the described used electrolytic salt of propylene carbonate ester group electrolyte that contains additive is electrolytic salt commonly used in the present commercialization electrolyte system, is lithium hexafluoro phosphate (LiPF
6), lithium perchlorate (LiClO
4), di-oxalate lithium borate (LiBC
4O
8, LiBOB), LiBF4 (LiBF
4), trifluoromethyl sulfonic acid lithium (LiCF
3SO
3), tetraethyl ammonium tetrafluoroborate ((C
2H
5)
4NBF
4), two (trifluoromethane sulfonic acid acyl) imine lithium (LiN (CF
3SO
2)
2), methyltriethylammonitetrafluoroborate tetrafluoroborate (CH
3(C
2H
5)
3NBF
4) in a kind of or its combination.
4. one kind by the described propylene carbonate ester group electrolyte that contains additive of one of claim 1-3.
5. by the application of propylene carbonate ester group electrolyte in lithium ion battery that contains additive claimed in claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102726211A CN103000942A (en) | 2011-09-15 | 2011-09-15 | Additive promoting graphite cathode to generate solid electrolyte interfacial film, and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102726211A CN103000942A (en) | 2011-09-15 | 2011-09-15 | Additive promoting graphite cathode to generate solid electrolyte interfacial film, and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103000942A true CN103000942A (en) | 2013-03-27 |
Family
ID=47929250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102726211A Pending CN103000942A (en) | 2011-09-15 | 2011-09-15 | Additive promoting graphite cathode to generate solid electrolyte interfacial film, and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103000942A (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406119A (en) * | 2014-06-30 | 2016-03-16 | 比亚迪股份有限公司 | Lithium ion battery electrolyte and lithium ion battery containing electrolyte |
| CN106935906A (en) * | 2017-04-28 | 2017-07-07 | 张家港市国泰华荣化工新材料有限公司 | A kind of functional form polymer dielectric and its application in lithium ion battery |
| CN108390096A (en) * | 2018-03-01 | 2018-08-10 | 中南大学 | A kind of application of tetrafluoroborate, composite electrolyte and composite positive pole comprising tetrafluoroborate |
| CN110574210A (en) * | 2017-07-14 | 2019-12-13 | 株式会社Lg化学 | Nonaqueous electrolyte solution additive and nonaqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
| CN110707360A (en) * | 2019-10-21 | 2020-01-17 | 广州天赐高新材料股份有限公司 | Lithium ion battery electrolyte, lithium ion battery and application |
| CN110998956A (en) * | 2017-11-22 | 2020-04-10 | 株式会社Lg化学 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery containing the same |
| CN111244545A (en) * | 2020-01-20 | 2020-06-05 | 珠海冠宇电池有限公司 | Overcharge-preventing electrolyte and lithium ion battery using same |
| WO2020149705A1 (en) * | 2019-01-17 | 2020-07-23 | 주식회사 엘지화학 | Electrolyte for lithium secondary battery, and lithium secondary battery comprising same |
| WO2021071109A1 (en) * | 2019-10-07 | 2021-04-15 | 삼성에스디아이 주식회사 | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN112909339A (en) * | 2021-03-23 | 2021-06-04 | 深圳赛骄阳能源科技股份有限公司 | Propylene carbonate-based electrolyte and lithium ion battery containing same |
| CN113394450A (en) * | 2021-07-09 | 2021-09-14 | 杉杉新材料（衢州）有限公司 | Lithium cobaltate high-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113517470A (en) * | 2021-05-13 | 2021-10-19 | 杉杉新材料（衢州）有限公司 | High-nickel high-voltage ternary lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113614976A (en) * | 2019-01-17 | 2021-11-05 | 株式会社Lg新能源 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN113678298A (en) * | 2019-02-28 | 2021-11-19 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| EP3893312A4 (en) * | 2019-01-17 | 2022-03-09 | Lg Energy Solution, Ltd. | ANHYDROUS ELECTROLYTE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT |
| EP3902051A4 (en) * | 2019-01-25 | 2022-03-23 | Lg Energy Solution, Ltd. | ELECTROLYTE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT |
| CN114373987A (en) * | 2020-10-15 | 2022-04-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN114583272A (en) * | 2022-02-16 | 2022-06-03 | 华南师范大学 | An electrolyte and lithium secondary battery |
| WO2023059037A1 (en) * | 2021-10-07 | 2023-04-13 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
| WO2023121028A1 (en) * | 2021-12-21 | 2023-06-29 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte comprising additive for non-aqueous electrolyte, and lithium secondary battery comprising same |
| WO2023191235A1 (en) * | 2022-04-01 | 2023-10-05 | 삼성에스디아이주식회사 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
-
2011
- 2011-09-15 CN CN2011102726211A patent/CN103000942A/en active Pending
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105406119A (en) * | 2014-06-30 | 2016-03-16 | 比亚迪股份有限公司 | Lithium ion battery electrolyte and lithium ion battery containing electrolyte |
| CN105406119B (en) * | 2014-06-30 | 2018-05-29 | 比亚迪股份有限公司 | A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte |
| CN106935906A (en) * | 2017-04-28 | 2017-07-07 | 张家港市国泰华荣化工新材料有限公司 | A kind of functional form polymer dielectric and its application in lithium ion battery |
| CN110574210A (en) * | 2017-07-14 | 2019-12-13 | 株式会社Lg化学 | Nonaqueous electrolyte solution additive and nonaqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
| CN110574210B (en) * | 2017-07-14 | 2022-08-05 | 株式会社Lg化学 | Additive for non-aqueous electrolyte solution, non-aqueous electrolyte solution for lithium secondary battery comprising the same, and lithium secondary battery |
| CN110998956B (en) * | 2017-11-22 | 2021-12-10 | 株式会社Lg化学 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN110998956A (en) * | 2017-11-22 | 2020-04-10 | 株式会社Lg化学 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery containing the same |
| CN108390096A (en) * | 2018-03-01 | 2018-08-10 | 中南大学 | A kind of application of tetrafluoroborate, composite electrolyte and composite positive pole comprising tetrafluoroborate |
| US12119448B2 (en) | 2019-01-17 | 2024-10-15 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
| JP2022516773A (en) * | 2019-01-17 | 2022-03-02 | エルジー エナジー ソリューション リミテッド | Electrolytes for lithium secondary batteries and lithium secondary batteries containing them |
| JP7226891B2 (en) | 2019-01-17 | 2023-02-21 | エルジー エナジー ソリューション リミテッド | Electrolyte for lithium secondary battery and lithium secondary battery containing the same |
| US12062759B2 (en) | 2019-01-17 | 2024-08-13 | Lg Energy Solution, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN113614976B (en) * | 2019-01-17 | 2023-12-19 | 株式会社Lg新能源 | Non-aqueous electrolyte solution for lithium secondary batteries and lithium secondary batteries containing the same |
| CN113614976A (en) * | 2019-01-17 | 2021-11-05 | 株式会社Lg新能源 | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| WO2020149705A1 (en) * | 2019-01-17 | 2020-07-23 | 주식회사 엘지화학 | Electrolyte for lithium secondary battery, and lithium secondary battery comprising same |
| EP3893312A4 (en) * | 2019-01-17 | 2022-03-09 | Lg Energy Solution, Ltd. | ANHYDROUS ELECTROLYTE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT |
| EP3902051A4 (en) * | 2019-01-25 | 2022-03-23 | Lg Energy Solution, Ltd. | ELECTROLYTE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT |
| US12183885B2 (en) | 2019-01-25 | 2024-12-31 | Lg Energy Solution, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| US12266761B2 (en) | 2019-02-28 | 2025-04-01 | Lg Energy Solution, Ltd. | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN113678298A (en) * | 2019-02-28 | 2021-11-19 | 株式会社Lg新能源 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| EP3913719A4 (en) * | 2019-02-28 | 2022-03-23 | Lg Energy Solution, Ltd. | ELECTROLYTE FOR LITHIUM SECONDARY BATTERY AND LITHIUM SECONDARY BATTERY WITH IT |
| JP2022521585A (en) * | 2019-02-28 | 2022-04-11 | エルジー エナジー ソリューション リミテッド | Electrolytes for lithium secondary batteries and lithium secondary batteries containing them |
| JP7233801B2 (en) | 2019-02-28 | 2023-03-07 | エルジー エナジー ソリューション リミテッド | Electrolyte for lithium secondary battery and lithium secondary battery containing the same |
| WO2021071109A1 (en) * | 2019-10-07 | 2021-04-15 | 삼성에스디아이 주식회사 | Electrolyte solution for lithium secondary battery and lithium secondary battery comprising same |
| CN114556657A (en) * | 2019-10-07 | 2022-05-27 | 三星Sdi株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN110707360A (en) * | 2019-10-21 | 2020-01-17 | 广州天赐高新材料股份有限公司 | Lithium ion battery electrolyte, lithium ion battery and application |
| CN111244545A (en) * | 2020-01-20 | 2020-06-05 | 珠海冠宇电池有限公司 | Overcharge-preventing electrolyte and lithium ion battery using same |
| CN114373987A (en) * | 2020-10-15 | 2022-04-19 | 宁德新能源科技有限公司 | Electrolyte solution, electrochemical device, and electronic device |
| CN114373987B (en) * | 2020-10-15 | 2024-04-19 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic device |
| CN112909339A (en) * | 2021-03-23 | 2021-06-04 | 深圳赛骄阳能源科技股份有限公司 | Propylene carbonate-based electrolyte and lithium ion battery containing same |
| CN113517470A (en) * | 2021-05-13 | 2021-10-19 | 杉杉新材料（衢州）有限公司 | High-nickel high-voltage ternary lithium ion battery non-aqueous electrolyte and lithium ion battery |
| CN113394450A (en) * | 2021-07-09 | 2021-09-14 | 杉杉新材料（衢州）有限公司 | Lithium cobaltate high-voltage lithium ion battery non-aqueous electrolyte and lithium ion battery |
| WO2023059037A1 (en) * | 2021-10-07 | 2023-04-13 | 주식회사 엘지에너지솔루션 | Lithium secondary battery |
| WO2023121028A1 (en) * | 2021-12-21 | 2023-06-29 | 주식회사 엘지에너지솔루션 | Non-aqueous electrolyte comprising additive for non-aqueous electrolyte, and lithium secondary battery comprising same |
| CN114583272A (en) * | 2022-02-16 | 2022-06-03 | 华南师范大学 | An electrolyte and lithium secondary battery |
| WO2023191235A1 (en) * | 2022-04-01 | 2023-10-05 | 삼성에스디아이주식회사 | Electrolyte for lithium secondary battery and lithium secondary battery comprising same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103000942A (en) | Additive promoting graphite cathode to generate solid electrolyte interfacial film, and application thereof | |
| CN111883839B (en) | High-voltage electrolyte and lithium ion battery based on same | |
| CN102394314A (en) | Lithium ion battery electrolyte and lithium ion secondary battery | |
| CN103384017B (en) | A kind of nonaqueous electrolytic solution of high-voltage lithium ion batteries | |
| CN110120554B (en) | Electrolyte and secondary battery containing same | |
| CN110416616B (en) | A lithium-sulfur battery electrolyte and its application | |
| US20170294677A1 (en) | Fluorine-Substituted Propylene Carbonate-Based Electrolytic Solution and Lithium-Ion Battery | |
| CN109888384B (en) | Electrolyte and battery containing the same | |
| CN111864260B (en) | Ether gel electrolyte and preparation method and application thereof | |
| CN107017433B (en) | Nonaqueous electrolytic solution and lithium ion battery | |
| CN109935908B (en) | Low-concentration lithium salt electrolyte and lithium secondary battery comprising same | |
| CN104466247A (en) | Nonaqueous electrolyte and lithium ion battery utilizing same | |
| CN105514489A (en) | Electrolyte and lithium ion battery containing electrolyte | |
| CN105449279A (en) | Non-aqueous electrolyte solution and lithium-ion battery using same | |
| CN113054251B (en) | Electrolyte suitable for high-voltage system lithium ion battery and lithium ion battery | |
| CN108258317B (en) | Lithium-sulfur battery | |
| CN112490507A (en) | Lithium-sulfur battery electrolyte and preparation method and application thereof | |
| CN109037776A (en) | Electrolyte and battery comprising same | |
| CN113113668B (en) | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery | |
| CN115133125A (en) | Method for improving solubility of lithium salt additive and electrolyte containing lithium salt additive | |
| CN104577201A (en) | Electrolyte for lithium-carbon fluoride battery | |
| CN111952669B (en) | Lithium-sulfur battery and composite solvent and electrolyte thereof | |
| CN114552016A (en) | Electrolyte additive, lithium ion battery electrolyte and lithium ion battery | |
| CN110165299B (en) | Lithium-sulfur battery, electrolyte and application thereof | |
| CN107706456A (en) | Lithium fluorocarbon battery electrolyte of mixed solvent containing dimethyl sulfoxide and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130327 |