CN116941088A - Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same - Google Patents
Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same Download PDFInfo
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- CN116941088A CN116941088A CN202280018013.4A CN202280018013A CN116941088A CN 116941088 A CN116941088 A CN 116941088A CN 202280018013 A CN202280018013 A CN 202280018013A CN 116941088 A CN116941088 A CN 116941088A
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- lithium secondary
- secondary battery
- lithium
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- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002642 lithium compounds Chemical class 0.000 claims description 2
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- HCLGRIKAYORQCQ-UHFFFAOYSA-M P(=O)([O-])(O)O.[Li+].C(C(=O)O)(=O)OF.C(C(=O)O)(=O)OF Chemical compound P(=O)([O-])(O)O.[Li+].C(C(=O)O)(=O)OF.C(C(=O)O)(=O)OF HCLGRIKAYORQCQ-UHFFFAOYSA-M 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- 229910008326 Si-Y Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006773 Si—Y Inorganic materials 0.000 description 1
- 229910020997 Sn-Y Inorganic materials 0.000 description 1
- 229910008859 Sn—Y Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 1
- RLTFLELMPUMVEH-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[V+5] Chemical compound [Li+].[O--].[O--].[O--].[V+5] RLTFLELMPUMVEH-UHFFFAOYSA-N 0.000 description 1
- ZYXUQEDFWHDILZ-UHFFFAOYSA-N [Ni].[Mn].[Li] Chemical compound [Ni].[Mn].[Li] ZYXUQEDFWHDILZ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- SVPZJHKVRMRREG-UHFFFAOYSA-N cyclopentanecarbonitrile Chemical compound N#CC1CCCC1 SVPZJHKVRMRREG-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011326 fired coke Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 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 description 1
- 229910021450 lithium metal oxide Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 208000020960 lithium transport Diseases 0.000 description 1
- 229910000686 lithium vanadium oxide Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006051 mesophase pitch carbide Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical compound CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CBIQXUBDNNXYJM-UHFFFAOYSA-N tris(2,2,2-trifluoroethyl) phosphite Chemical compound FC(F)(F)COP(OCC(F)(F)F)OCC(F)(F)F CBIQXUBDNNXYJM-UHFFFAOYSA-N 0.000 description 1
- VMZOBROUFBEGAR-UHFFFAOYSA-N tris(trimethylsilyl) phosphite Chemical compound C[Si](C)(C)OP(O[Si](C)(C)C)O[Si](C)(C)C VMZOBROUFBEGAR-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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 present application relates to a nonaqueous electrolyte for a lithium secondary battery and a lithium secondary battery including the same. Specifically, the nonaqueous electrolyte for a lithium secondary battery includes a lithium salt, an organic solvent, and a compound represented by formula 1 to form a robust SEI film, thereby improving the performance of the battery.
Description
Technical Field
Cross Reference to Related Applications
The present application claims priority from korean patent application No. 10-2021-013188, filed on 10 months 12 of 2021, and from korean patent application No. 10-2022-0127218, filed on 5 of 10 months 2022, the disclosures of which are incorporated herein by reference.
Technical Field
The present application relates to a nonaqueous electrolyte for a lithium secondary battery, which contains an additive that can form a robust SEI film, and a lithium secondary battery capable of suppressing an increase in initial resistance and improving output characteristics by containing the same.
Background
With the recent development of information society, personal IT devices and computer networks have been developed, and the dependence of the entire society on electric energy has increased, so that development of a technology for efficiently storing and utilizing electric energy has been required.
Among the developed technologies, a secondary battery is the most suitable technology for various applications, and among them, a lithium ion battery that can be miniaturized to be suitable for personal IT equipment and has the highest energy density is the focus of attention.
A lithium ion battery is composed of a positive electrode containing a lithium-containing transition metal oxide, a negative electrode containing a carbon-based material capable of storing lithium (for example, graphite), an electrolyte as a medium for transporting lithium ions, and a separator. In order to improve the electrochemical characteristics of the battery, it is important to appropriately select these components.
On the other hand, when the lithium secondary battery is operated under high temperature conditions, the PF 6 - The anions may be derived from lithium salts (e.g., liPF) 6 ) Thermal decomposition to produce Lewis acids (e.g. PF 5 ) Which reacts with moisture to form HF. Such as PF 5 And HF or the like may not only destroy the film formed on the electrode surface but also cause decomposition of the organic solvent. Thus, side reactions between the exposed surface of the electrode and the electrolyte result in elution of transition metal ions from the positive electrode. Therefore, as the transition metal ions of the positive electrode are eluted, the lattice structure of the positive electrode becomes unstable, thereby causing active oxygen to be generated in the positive electrode. This further promotes the decomposition of the electrolyte solvent, thereby accelerating the generation of gas. In addition, when eluted transition metal ions move to the anode through an electrolyte and then are electrodeposited on the surface of the anode, additional lithium ion consumption is caused due to destruction and regeneration reaction of a Solid Electrolyte Interface (SEI) film, and an increase in resistance and a deterioration in capacity are caused.
Accordingly, various researches are currently being conducted to develop a secondary battery that maintains the passivation capability of the SEI film even under high temperature conditions to achieve excellent performance.
Disclosure of Invention
Technical problem
In order to solve the above problems, the present application aims to provide a nonaqueous electrolyte for a lithium secondary battery that contains an additive capable of providing an SEI enhancing effect, and a lithium secondary battery that has improved output characteristics and suppressed increase in battery resistance by containing the electrolyte.
Technical proposal
According to one embodiment of the present application, there is provided a nonaqueous electrolytic solution for a lithium secondary battery, which includes a lithium salt, a nonaqueous organic solvent, and a compound represented by the following formula 1.
[ 1]
In the above description of the method 1,
R 1 and R is 2 Each independently is an alkylene group having 1 to 10 carbon atoms, R 3 Is an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
According to another aspect of the present application, there is provided a lithium secondary battery including: a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and a separator disposed between the negative electrode and the positive electrode; the nonaqueous electrolyte for lithium secondary batteries of the present application.
Advantageous effects
Since the compound represented by formula 1 contained in the non-aqueous electrolyte for a lithium secondary battery of the present application contains a propargyl group (-c≡c-) and a fluorocarbon functional group substituted with one or more fluorine elements in the structure, it can be reduced prior to the organic solvent, forming a low-resistance SEI film containing a fluorocarbon component on the electrode surface, thereby suppressing additional reductive decomposition of the non-aqueous electrolyte.
Therefore, when such a nonaqueous electrolytic solution for a lithium secondary battery is contained, a self-discharge reaction of the negative electrode can be prevented, and an increase in initial resistance can be suppressed, so that a lithium secondary battery having improved output characteristics at both low temperature and low temperature can be realized.
Detailed Description
First, before describing the present application, it should be understood that words or terms used in the specification and claims should not be construed as meanings defined in commonly used dictionaries, and it should be further understood that words or terms should be interpreted as having meanings consistent with their meanings in the relevant technical background and technical ideas of the present application based on the principle that the inventors can properly define the meanings of the words or terms to best explain the present application. Meanwhile, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the application. The singular also includes the plural unless the context clearly indicates otherwise. It will be understood that terms, such as "comprises," "comprising," "includes," or "having," when used herein, are intended to specify the presence of stated features, integers, steps, elements, or groups thereof, but do not preclude the presence or addition of other features, integers, steps, elements, or groups thereof.
In the present specification, unless explicitly stated otherwise, the expression "%" means% by weight.
Before describing the present application, the expressions "a" and "b" in the specification of "a to b carbon atoms" respectively represent the number of carbon atoms contained in a specific functional group. I.e., the functional group may include "a" to "b" carbon atoms.
In addition, unless otherwise defined in the specification, the expression "substituted" means that at least one hydrogen bonded to carbon is substituted with an element other than hydrogen (e.g., an alkyl group having 1 to 5 carbon atoms or a fluorine element).
Hereinafter, the present application will be described in more detail.
In general, in the case of a lithium secondary battery, a film having passivation ability may be formed on the surfaces of a negative electrode and a positive electrode while a nonaqueous electrolyte is decomposed during initial charge and discharge to secure high temperature storage characteristics. However, the film is widely used for lithium salt (LIPF 6 Etc.) of the lewis acid materials (e.g., HF and PF) produced by thermal decomposition of the same 5 ) And is deteriorated. That is, when the transition metal element is eluted from the positive electrode due to attack of the lewis acid material, the surface resistance of the electrode may increase due to the change of the surface structure, and the theoretical capacity may decrease as the metal element as the redox center is lost, and thus the expression capacity may decrease. In addition, the transition metal ions eluted in this way may not only be electrodeposited on the negative electrode where reaction occurs in a strong reduction potential range to consume electrons, but may also damage the film during electrodeposition, exposing the surface of the negative electrode, thereby causing additional electrolyte decomposition reaction. Therefore, the negative electrode resistance and the irreversible capacity increase, resulting in continuous degradation of the output characteristics of the battery cell.
Accordingly, in order to form a stable film, the present application aims to provide a nonaqueous electrolyte for a lithium secondary battery capable of forming an SEI film of low resistance by containing a compound having a propargyl group (-c≡c-) substituted with one or more fluorine-containing fluorocarbon functional groups in the molecular structure as an additive, and a lithium secondary battery containing the same.
Nonaqueous electrolyte for lithium secondary battery
The present application provides a nonaqueous electrolyte for a lithium secondary battery, which comprises a lithium salt, a nonaqueous organic solvent, and a compound represented by the following formula 1.
[ 1]
In the formula (1) of the present application,
R 1 and R is 2 Each independently is an alkylene group having 1 to 10 carbon atoms, R 3 Is an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
(1) Lithium salt
First, a lithium salt will be described as follows.
In the nonaqueous electrolytic solution for a lithium secondary battery according to the embodiment of the present application, as the lithium salt, any lithium salt commonly used for an electrolytic solution of a lithium secondary battery may be used without limitation, and for example, the lithium salt may include Li + As the cation, and at least one selected from the group consisting of: f (F) - 、Cl - 、Br - 、I - 、NO 3 - 、N(CN) 2 - 、BF 4 - 、ClO 4 - 、AlO 4 - 、AlCl 4 - 、PF 6 - 、SbF 6 - 、AsF 6 - 、B 10 Cl 10 - 、BF 2 C 2 O 4 - 、BC 4 O 8 - 、PF 4 C 2 O 4 - 、PF 2 C 4 O 8 - 、(CF 3 ) 2 PF 4 - 、(CF 3 ) 3 PF 3 - 、(CF 3 ) 4 PF 2 - 、(CF 3 ) 5 PF - 、(CF 3 ) 6 P - 、CF 3 SO 3 - 、C 4 F 9 SO 3 - 、CF 3 CF 2 SO 3 - 、(CF 3 SO 2 ) 2 N - 、(FSO 2 ) 2 N - 、CF 3 CF 2 (CF 3 ) 2 CO - 、(CF 3 SO 2 ) 2 CH - 、CH 3 SO 3 - 、CF 3 (CF 2 ) 7 SO 3 - 、CF 3 CO 2 - 、CH 3 CO 2 - 、SCN - Sum (CF) 3 CF 2 SO 2 ) 2 N - . In particular, the lithium salt may include at least one selected from the group consisting of: liCl, liBr, liI, liBF 4 、LiClO 4 、LiAlO 4 、LiAlCl 4 、LiPF 6 、LiSbF 6 、LiAsF 6 、LiB 10 Cl 10 、LiBOB(LiB(C 2 O 4 ) 2 )、LiCF 3 SO 3 、LiTFSI(LiN(SO 2 CF 3 ) 2 )、LiFSI(LiN(SO 2 F) 2 )、LiCH 3 SO 3 、LiCF 3 CO 2 、LiCH 3 CO 2 And LiBETI (LiN (SO) 2 CF 2 CF 3 ) 2 ). In particular, the lithium salt may comprise a medium single material selected from the group consisting of: liBF 4 、LiClO 4 、LiPF 6 、LiBOB(LiB(C 2 O 4 ) 2 )、LiCF 3 SO 3 、LiTFSI(LiN(SO 2 CF 3 ) 2 )、LiFSI(LiN(SO 2 F) 2 ) And LiBETI (LiN (SO) 2 CF 2 CF 3 ) 2 ) Or a mixture of two or more thereof. More specifically, the lithium salt may include LiPF 6 。
The lithium salt may be appropriately changed within a normal use range, but may be present in the electrolyte at a concentration of 0.8M to 3.0M, specifically 1.0M to 3.0M, to obtain an optimal effect of forming a film for preventing corrosion of the electrode surface.
In the case where the concentration of the lithium salt satisfies the above range, the viscosity of the nonaqueous electrolytic solution can be controlled, so that optimal impregnation can be achieved, and the effect of improving the capacity characteristics and cycle characteristics of the lithium secondary battery can be obtained by improving the mobility of lithium ions.
(2) Nonaqueous organic solvents
In addition, the nonaqueous organic solvent will be described below.
The nonaqueous organic solvent may include at least one selected from the group consisting of a cyclic carbonate compound, a linear carbonate compound, and a linear ester compound.
The cyclic carbonate compound is a high-viscosity organic solvent and is capable of well dissociating a lithium salt in the electrolyte due to a high dielectric constant, wherein a specific example thereof may be at least one organic solvent selected from the group consisting of: ethylene Carbonate (EC), propylene Carbonate (PC), 1, 2-butylene carbonate, 2, 3-butylene carbonate, 1, 2-pentylene carbonate, 2, 3-pentylene carbonate, vinylene carbonate, and at least one of ethylene carbonate and Propylene Carbonate (PC) may be included therein.
Further, the linear carbonate compound is a compound having a low viscosity and a low dielectric constant, wherein a typical example thereof may be at least one organic solvent selected from the group consisting of: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl Methyl Carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate, and may include, in particular, ethyl Methyl Carbonate (EMC).
In addition, specific examples of the linear ester compound may include one selected from the group consisting of: methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate, may generally include at least one of ethyl propionate and propyl propionate.
In the present application, in order to prepare an electrolyte having high ionic conductivity, a mixed solvent of a cyclic carbonate compound, a linear carbonate compound, and a linear ester compound may be used as a nonaqueous organic solvent. Meanwhile, the content of the cyclic carbonate compound may be 50% by volume or less, specifically 40% by volume or less, preferably 30% by volume or less, based on the total content of the nonaqueous organic solvent of the present application.
In addition, the nonaqueous organic solvent may further include at least one of a cyclic ester compound, an ether compound, an amide compound, and a nitrile compound. The cyclic ester compound may be at least one selected from the group consisting of: gamma-butyrolactone, gamma-valerolactone, gamma-caprolactone, sigma-valerolactone and epsilon-caprolactone.
Further, as the ester compound, any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether and ethylpropyl ether, or a mixture of two or more thereof may be used.
Further, the nitrile compound may be at least one selected from the group consisting of: acetonitrile, propionitrile, butyronitrile, valeronitrile, octanonitrile, heptanenitrile, cyclopentanitrile, cyclohexanecarbonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorobenzonitrile and 4-fluorobenzonitrile.
Meanwhile, unless otherwise specified, the rest of the nonaqueous electrolyte of the present application except for the lithium salt and the additive may be a nonaqueous organic solvent.
(3) Electrolyte additive
The nonaqueous electrolyte for lithium secondary batteries of the present application may include a compound represented by the following formula 1 as an electrolyte additive.
[ 1]
In the formula (1) of the present application,
R 1 and R is 2 Each independently is an alkylene group having 1 to 10 carbon atoms, R 3 Is an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
Specifically, the compound represented by formula 1 includes one propargyl functional group in its structure, and is easily reduced and decomposed at the surface of the anode, thereby forming an SEI film having low resistance and high passivation ability. Accordingly, not only the durability of the anode itself can be improved, but also the electrodeposition of the transition metal on the surface of the anode can be prevented, thereby preventing the self-discharge reaction of the graphite-based and silicon-based anode due to the additional reduction and decomposition reaction of the electrolyte due to the instability of the SEI film.
Further, the compound represented by formula 1 suppresses elution of metal impurities from the positive electrode by containing a fluorocarbon functional group substituted with one or more fluorine elements at the structural end, and suppresses electrodeposition and precipitation of eluted metal ions on the negative electrode, thereby forming a film having reliable oxidation resistance on the positive electrode surface, thereby preventing internal short circuits.
Accordingly, the non-aqueous electrolyte of the present application includes the compound represented by formula 1 (containing a fluorocarbon functional group substituted with one or more fluorine and a propargyl group) having excellent flame retardancy and incombustibility as an additive, thereby forming a stable SEI film having low resistance, thereby suppressing additional reductive decomposition of the non-aqueous electrolyte, and also preventing self-discharge reaction of the anode. Accordingly, it is possible to manufacture a lithium secondary battery that suppresses an increase in initial resistance and has improved room temperature output characteristics and low temperature output characteristics.
Meanwhile, in the compound represented by formula 1, R 1 And R is 2 Can each independently be an alkylene group having 1 to 5 carbon atoms, R 3 May be an alkyl group having 3 to 20 carbon atoms substituted with one or more fluorine atoms.
In addition, in the compound represented by formula 1, R 1 And R is 2 Can each independently be an alkylene group having 1 to 3 carbon atoms, R 3 May be an alkyl group having 3 to 15 carbon atoms substituted with one or more fluorine atoms.
Specifically, in the compound represented by formula 1, R 3 May be an alkyl group having 3 to 10 carbon atoms substituted with one or more fluorine atoms.
Preferably, the compound represented by formula 1 may be at least one of compounds represented by the following formulas 1a to 1 c.
[ 1a ]
[ 1b ]
[ 1c ]
The content of the compound represented by formula 1 may be 0.01 to 10.0 wt% based on the total weight of the nonaqueous electrolytic solution for lithium secondary battery.
In the case where the content of the compound represented by formula 1 is within the above range, an SEI film of low resistance is formed on the surface of the anode while minimizing side reactions, capacity degradation, and resistance increase caused by additives, and thus the lithium transport effect can be improved. The self-discharge reaction of the anode can be prevented by suppressing the additional reductive decomposition reaction of the electrolyte.
Specifically, in the case where the content of the compound represented by formula 1 is 0.01 wt% or more, a stable film may be formed during the operation of the battery. In the case where the content of the compound represented by formula 1 is 10.0 wt% or less, the viscosity of the nonaqueous electrolytic solution can be controlled, so that optimal impregnation can be achieved, an increase in battery resistance due to decomposition of the additive can be effectively suppressed, and ion conductivity in the battery can be further increased to prevent deterioration of output characteristics.
Specifically, in the nonaqueous electrolytic solution, the content of the compound represented by formula 1 may be 0.1 to 6.0% by weight, specifically 0.5 to 5% by weight, preferably 0.5 to 3% by weight.
(4) Other additives
Meanwhile, the nonaqueous electrolyte for lithium secondary batteries of the present application may include other additional additives in addition to the compound represented by formula 1, if necessary, to prevent collapse of the negative electrode from occurring due to decomposition of the nonaqueous electrolyte in a high power environment, or to further improve low-temperature high-rate discharge characteristics, high-temperature stability, overcharge prevention, and battery swelling inhibition effects at high temperatures.
Examples of the other additives may be at least one selected from the group consisting of: cyclic carbonate compounds, halogenated carbonate compounds, sultone compounds, sulfate compounds, phosphate compounds or phosphite compounds, borate compounds, nitrile compounds, benzene compounds, amine compounds, silane compounds and lithium compounds.
The cyclic carbonate compound may include Vinylene Carbonate (VC) or Vinyl Ethylene Carbonate (VEC).
The halogenated carbonate compound may be fluoroethylene carbonate (FEC), for example.
The sultone-based compound may be, for example, at least one compound selected from the group consisting of: 1, 3-Propane Sultone (PS), 1, 4-butane sultone, ethane sultone, 1, 3-propylene sultone (PRS), 1, 4-butene sultone and 1-methyl-1, 3-propylene sultone.
For example, the sulfate compound may be ethylene sulfate (ESa), trimethylene sulfate (TMS) or trimethylene methylsulfate (MTMS).
For example, the phosphate compound or phosphite compound may be at least one compound selected from the group consisting of: lithium difluoro (bisoxalate) phosphate, lithium difluoro phosphate, tris (trimethylsilyl) phosphite, tris (2, 2-trifluoroethyl) phosphate and tris (trifluoroethyl) phosphite.
The borate/salt compound can be tetraphenyl borate and oxalyl lithium difluoroborate (LiODFB) or lithium bis (oxalate) borate (LiB (C) 2 O 4 ) 2 ，LiBOB)。
For example, the nitrile compound may be at least one compound selected from the group consisting of: succinonitrile (SN), adiponitrile, acetonitrile, propionitrile, butyronitrile, valeronitrile, octanonitrile, heptanenitrile, cyclopentanonitrile, cyclohexanonitrile, 2-fluorobenzonitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorobenzonitrile and 4-fluorobenzonitrile.
The benzene compound can be fluorobenzene, the amine compound can be triethanolamine or ethylenediamine, and the silane compound can be tetravinyl silane.
The lithium salt compound is a compound different from the lithium salt contained in the nonaqueous electrolyte, wherein the lithium salt compound may contain lithium difluorophosphate (LiPO) 2 F 2 ) Or LiBF 4 。
Among these other additives, when Bao Tansuan vinylene, vinyl ethylene carbonate or succinonitrile, a more stable SEI film may be formed on the surface of the negative electrode during initial activation of the secondary battery. In addition, when LiBF is included 4 In this case, the high-temperature stability of the secondary battery can be improved by suppressing gas generation caused by decomposition of the electrolyte during high-temperature storage.
Two or more compounds may be mixed to be used as other additives, and the total content of the compound represented by formula 1 and other additives may be 50% by weight or less, specifically 0.05% by weight to 20% by weight, specifically 0.05% by weight to 10% by weight, based on the total weight of the nonaqueous electrolytic solution. When the amount of the other additive satisfies the above range, the low temperature output characteristics of the battery may be improved, and the high temperature storage characteristics and the high temperature life characteristics may be more effectively improved. It is also possible to prevent the occurrence of side reactions of the battery caused by the remaining additives after the reaction.
Lithium secondary battery
Further, in another embodiment of the present application, there is provided a lithium secondary battery comprising the nonaqueous electrolytic solution for a lithium secondary battery of the present application.
Specifically, the lithium secondary battery may include: a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, and a separator disposed between the positive electrode and the negative electrode; the nonaqueous electrolyte for lithium secondary batteries.
Meanwhile, after an electrode assembly in which a positive electrode, a separator, and a negative electrode are sequentially stacked and contained in a battery case, the lithium secondary battery of the present application may be prepared by injecting the non-aqueous electrolyte of the present application.
The lithium secondary battery of the present application may be prepared and used according to conventional methods known in the art, and the preparation method of the lithium secondary battery of the present application is specifically described as follows.
(1) Positive electrode
The positive electrode of the present application may include a positive electrode active material layer including a positive electrode active material, and if necessary, the positive electrode active material layer may further include a conductive agent and/or a binder.
The positive electrode active material is a compound capable of reversibly intercalating and deintercalating lithium, wherein the positive electrode active material may include a lithium transition metal oxide containing lithium and at least one metal selected from cobalt, manganese, nickel, or aluminum, and may include, in particular, lithium manganese-based oxides, lithium iron phosphate, and lithium nickel manganese cobalt-based oxides (for example, li (Ni p Co q Mn r1 )O 2 Wherein 0 < p < 1,0 < q < 1,0 < r1 < 1, p+q+r1=1).
In particular, the lithium manganese-based oxide may be LiMnO 2 Or LiMn 2 O 4 The lithium iron phosphate may be LiFePO 4 。
Further, the lithium nickel manganese cobalt-based oxide may be at least one selected from the group consisting of: li (Ni) 1/3 Mn 1/ 3 Co 1/3 )O 2 、Li(Ni 0.6 Mn 0.2 Co 0.2 )O 2 、Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 、Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 And Li (Ni) 0.8 Mn 0.1 Co 0.1 )O 2 And desirably includes a transition metal oxide having a nickel content of 60atm% or more. That is, as the nickel content in the transition metal increases, a higher capacity can be achieved. Thus, the first and second substrates are bonded together,when the nickel content is 60atm% or more, it is more advantageous to achieve a high capacity. Such lithium composite oxide may be selected from the group consisting of Li (Ni 0.6 Mn 0.2 Co 0.2 )O 2 、Li(Ni 0.7 Mn 0.15 Co 0.15 )O 2 And Li (Ni) 0.8 Mn 0.1 Co 0.1 )O 2 At least one of the group consisting of.
Meanwhile, the positive electrode active material may include lithium cobalt-based oxide (e.g., liCoO) 2 Etc.), lithium nickel-based oxides (e.g., liNiO 2 Etc.), lithium nickel manganese-based oxides (e.g., liNi 1-Y Mn Y O 2 (wherein 0<Y<1)，LiMn 2-Z Ni Z O 4 (wherein 0<Z<2) Lithium nickel cobalt-based oxide (e.g., liNi) 1-Y1 Co Y1 O 2 (wherein 0<Y1<1) Lithium manganese cobalt based oxides (e.g. LiCo) 1-Y2 Mn Y2 O 2 (wherein 0<Y2<1)，LiMn 2-Z1 Co Z1 O 4 (wherein 0<Z1<2) Lithium nickel manganese cobalt-based oxide (e.g., li (Ni) p1 Co q1 Mn r2 )O 4 Where 0 < p1 < 2,0 < q1 < 2,0 < r2 < 2, p1+q1+r2=2), or lithium nickel cobalt transition metal (M) oxide (e.g. Li (Ni) p2 Co q2 Mn r3 M S2 )O 2 Wherein M is selected from the group consisting of Al, fe, V, cr, ti, ta, mg and Mo, and p2, q2, r3, and s2 are the atomic fractions of each individual element, wherein 0 < p2 < 1,0 < q2 < 1,0 < r3 < 1,0 < s2 < 1, p2+q2+r3+s2=1), and may contain any one or two or more of the compounds.
The positive electrode active material may be present in an amount of 90 to 99 wt%, specifically 93 to 98 wt%, based on the total weight of solids in the positive electrode active material layer.
The conductive agent is not particularly limited as long as it has conductivity without causing chemical changes in the battery, and for example, it is possible to use: conductive materials such as carbon powders, for example, carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; graphite powder, such as natural graphite, artificial graphite, or graphite having a well-developed crystal structure; conductive fibers, such as carbon fibers or metal fibers; conductive powders such as fluorocarbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or a polyphenylene derivative.
The content of the conductive agent is generally 1 to 30% by weight based on the total weight of solids in the positive electrode active material layer.
The binder is a component that contributes to the bonding between the positive electrode active material particles and the bonding between the positive electrode active material and the current collector, wherein the binder is generally added in an amount of 1 to 30% by weight based on the total weight of solids in the positive electrode active material layer. Examples of binders may be: fluororesin-based adhesives including polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE); rubber-based adhesives including Styrene Butadiene Rubber (SBR), acrylonitrile-butadiene rubber, or styrene-isoprene rubber; cellulosic binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, or regenerated cellulose; a polyol binder including polyvinyl alcohol; polyolefin adhesives, including polyethylene or polypropylene; polyimide-based adhesives; polyester-based compounds and silane-based binders.
The positive electrode of the present application as described above may be prepared by methods known in the art for preparing a positive electrode. For example, the positive electrode may be prepared by: wherein a positive electrode current collector is coated with a positive electrode slurry prepared by dissolving or dispersing a positive electrode active material, a binder and/or a conductive agent in a solvent, and then dried and rolled to form a positive electrode active material layer, or the positive electrode active material layer may be cast on a separate support, and then a film separated from the support is laminated on the positive electrode current collector.
The positive electrode current collector is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery, and may use, for example, stainless steel, aluminum, nickel, titanium, fired carbon, or aluminum or stainless steel surface-treated with one of carbon, nickel, titanium, silver, or the like.
The solvent may include an organic solvent such as NMP (N-methyl-2-pyrrolidone) or the like, and may be used in an amount such that a desired viscosity is obtained when the positive electrode active material, and optionally, the binder and the conductive agent are included. For example, the content thereof is such that the solid concentration in the active material slurry including the positive electrode active material and optional binder and conductive material is 10 to 70 wt%, preferably 20 to 60 wt%.
(2) Negative electrode
Next, the anode will be described.
The anode of the present application includes an anode active material layer containing an anode active material, and if necessary, the anode active material layer may further include a conductive agent and/or a binder. The anode active material may include at least one selected from the group consisting of: carbon materials capable of reversibly intercalating/deintercalating lithium ions, metals or alloys of lithium and the metal, metal composite oxides, materials that can be doped and dedoped with lithium, and transition metal oxides.
As the carbon material capable of reversibly intercalating/deintercalating lithium ions, a carbon-based anode active material commonly used in lithium ion secondary batteries may be used without particular limitation, and as typical examples, crystalline carbon and/or amorphous carbon may be used. Examples of crystalline carbon may be graphite, such as natural graphite or artificial graphite in an irregular, planar, flaky, spherical or fibrous form, and examples of amorphous carbon may be soft (low temperature sintered carbon) or hard carbon, mesophase pitch carbide and fired coke.
As the metal or the alloy of lithium and the metal, a metal selected from the group consisting of: cu, ni, na, K, rb, cs, fr, be, mg, ca, sr, si, sb, pb, in, zn, ba, ra, ge, al and Sn, or an alloy of lithium and the metal.
As the metal composite oxide, one selected from the group consisting of: pbO, pbO 2 、Pb 2 O 3 、Pb 3 O 4 、Sb 2 O 3 、Sb 2 O 4 、Sb 2 O 5 、GeO、GeO 2 、Bi 2 O 3 、Bi 2 O 4 、Bi 2 O 5 、Li x Fe 2 O 3 (0≤x≤1)、Li x WO 2 (0.ltoreq.x.ltoreq.1) and Sn x Me 1-x Me' y O z (Me: mn, fe, pb, ge; me' Al, B, P, si, elements of groups I, II and III of the periodic Table of the elements or halogen; 0)<x≤1；1≤y≤3；1≤z≤8)。
The materials that can be doped and undoped with lithium can include Si, siO x (0<x<2) A Si-Y alloy (wherein Y is an element selected from the group consisting of: alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, but not Si), sn, snO 2 And Sn-Y (wherein Y is an element selected from the group consisting of alkali metals, alkaline earth metals, group 13 elements, group 14 elements, transition metals, rare earth elements, and combinations thereof, but is not Sn), and SiO may be used 2 And mixtures of at least one thereof. The element Y may be selected from the group consisting of: mg, ca, sr, ba, ra, sc, Y, ti, zr, hf, rf, V, nb, ta, db, cr, mo, W, sg, tc, re, bh, fe, pb, ru, os, hs, rh, ir, pd, pt, cu, ag, au, zn, cd, B, al, ga, sn, in, ge, P, as, sb, bi, S, se, te, po, and combinations thereof.
The transition metal oxide may include lithium-containing titanium composite oxide (LTO), vanadium oxide, and lithium vanadium oxide.
The anode active material may be present in an amount of 80 to 99 wt% based on the total weight of solids in the anode active material layer.
The conductive agent is a component for further improving the conductivity of the anode active material, wherein the conductive agent may be added in an amount of 1 to 20% by weight based on the total weight of solids in the anode active material layer. Any conductive agent may be used without particular limitation as long as it has conductivity without causing adverse chemical changes in the battery, for example, the following conductive materials may be used, for example: graphite powders such as natural graphite and artificial graphite; carbon blacks such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; conductive fibers such as carbon fibers and metal fibers; conductive powders such as fluorocarbon powder, aluminum powder, and nickel powder; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; or a polyphenylene derivative.
The binder is a component that contributes to the bonding between the conductive agent, the active material, and the current collector, and is generally added in an amount of 1 to 30% by weight based on the total weight of solids in the anode active material layer. Examples of the binder may be a fluororesin-based binder including polyvinylidene fluoride (PVDF) or Polytetrafluoroethylene (PTFE); rubber-based adhesives including Styrene Butadiene Rubber (SBR), acrylonitrile-butadiene rubber, or styrene-isoprene rubber; cellulosic binders including carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, or regenerated cellulose; a polyol binder including polyvinyl alcohol; polyolefin adhesives, including polyethylene or polypropylene; polyimide-based adhesives; a polyester-based compound; and a silane-based adhesive.
The negative electrode may be prepared by methods known in the art for preparing a negative electrode. For example, the anode may be prepared by: the negative electrode current collector is coated with a negative electrode slurry prepared by dissolving or dispersing a negative electrode active material and optionally a binder and/or a conductive agent in a solvent, rolled and dried to form a negative electrode active material layer, or the negative electrode active material layer may be cast on a separate support, and then a film separated from the support is laminated on the negative electrode current collector.
The thickness of the negative electrode current collector is generally 3 μm to 500 μm. The negative electrode current collector is not particularly limited as long as it has high conductivity without causing adverse chemical changes in the battery, and copper or stainless steel surface-treated with one of carbon, nickel, titanium, silver, etc., and an aluminum-cadmium alloy may be used, for example, copper, stainless steel, aluminum, nickel, titanium, fired carbon. Like the positive electrode current collector, microscopic irregularities may be formed on the surface of the current collector to improve the adhesion of the negative electrode active material. For example, the negative electrode current collector may be used in various shapes, such as a film, a sheet, a foil, a net, a porous body, a foam body, a nonwoven fiber cloth body, and the like.
The solvent may include water or an organic solvent such as NMP and alcohol, and the amount thereof may be such that a desired viscosity is obtained when the anode active material, and optionally, a binder and a conductive agent are included. For example, the content of the solvent may be such that the concentration of solids in the anode slurry including the anode active material and optional binder and conductive agent is 50 to 75 wt%, preferably 50 to 65 wt%.
(3) Diaphragm
The lithium secondary battery of the present application includes a separator between a positive electrode and a negative electrode.
Since the separator separates the anode and the cathode and provides a moving path of lithium ions, wherein any separator may be used without particular limitation as long as the separator is generally used as a separator in a lithium secondary battery, in particular, a separator having high moisture retention ability for an electrolyte due to low resistance to electrolyte ion transfer is desirable.
Specifically, as the separator, a porous polymer film such as a porous polymer film prepared from a polyolefin-based polymer (e.g., an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer) or a laminated structure of two or more layers thereof is generally used.
As described above, the lithium secondary battery of the present application can be suitably used for portable devices such as mobile phones, notebook computers, and digital cameras, and electric vehicles such as Hybrid Electric Vehicles (HEVs).
Thus, according to another embodiment of the present application, there are provided a battery module including the lithium secondary battery as a unit cell and a battery pack including the battery module.
The battery module or the battery pack may be used as a power source for at least one of large and medium-sized devices: an electric tool; electric vehicles, including Electric Vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); or a power storage system. The shape of the lithium secondary battery of the present application is not particularly limited, but a cylindrical, prismatic, pouch, or coin type using a can may be used.
The lithium secondary battery of the present application can be used not only in battery cells used as a power source for small-sized devices, but also as unit cells of a large-and-medium-sized battery module including a plurality of battery cells.
Hereinafter, the present application will be described in detail according to specific examples. This application may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these exemplary embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the application to those skilled in the art.
Hereinafter, the present application will be described in detail according to specific examples.
Examples
Example 1.
(preparation of nonaqueous electrolyte)
In the LiPF process 6 Dissolved in a nonaqueous organic solvent in which Ethylene Carbonate (EC), propylene Carbonate (PC), ethyl Propionate (EP) and Propyl Propionate (PP) are mixed in a volume ratio of 20:10:20:50, so that LiPF 6 After a concentration of 1.0M, a nonaqueous electrolytic solution was prepared by adding 0.1 wt% of the compound represented by formula 1a and 0.5 wt% of vinylene carbonate (herein "VC"), 1.0 wt% of 1, 3-propane sultone (herein "PS"), 5.0 wt% of fluoroethylene carbonate (herein "FEC"), 1.0 wt% of succinonitrile (herein "SN"), and 0.5 wt% of lithium oxalyldifluoroborate (herein "LiODFB"), as other additives (refer to table 1 below).
(preparation of secondary cell)
Positive electrode active material particles (LiCoO) 2 ) A conductive agent (carbon black) and a binder (polyvinylidene fluoride) were added to N-methyl-2-pyrrolidone (NMP) as a solvent in a weight ratio of 97.5:1:1.5 to prepare a positive electrode slurry (solid content: 50.0 wt%). The positive electrode current collector (Al film) having a thickness of 15 μm was coated with the positive electrode slurry, dried, and then rolled to prepare a positive electrode.
The anode active material (graphite), binder (SBR-CMC) and conductive agent (carbon black) were added to water in a weight ratio of 95:3.5:1.5 to prepare an anode slurry (solid: 60 wt%). A negative electrode current collector (Cu thin film) having a thickness of 6 μm was coated with the negative electrode slurry, dried, and then rolled to prepare a negative electrode.
By stacking the positive electrodes in this order, the inorganic particles (Al 2 O 3 ) A polyolefin-based porous separator and a negative electrode to prepare an electrode assembly.
The above assembled electrode assembly was set in a battery case, and 6mL of the above prepared nonaqueous electrolyte was injected to prepare a lithium secondary battery.
Example 2.
In the LiPF process 6 Dissolving in non-aqueous organic solvent to obtain LiPF 6 A lithium secondary battery was prepared in the same manner as in example 1, except that a nonaqueous electrolytic solution was prepared by adding 1.0 wt% of the compound represented by formula 1a and 0.5 wt% of VEC, 1.0 wt% of PS, 5.0 wt% of FEC, 1.0 wt% of SN, and 0.5 wt% of LiODFB as other additives (refer to table 1 below).
Example 3.
In the LiPF process 6 Dissolving in non-aqueous organic solvent to obtain LiPF 6 A lithium secondary battery was prepared in the same manner as in example 1, except that a nonaqueous electrolytic solution was prepared by adding 5.0 wt% of the compound represented by formula 1a and 0.5 wt% of VEC, 1.0 wt% of PS, 5.0 wt% of FEC, 1.0 wt% of SN, and 0.5 wt% of LiODFB as other additives (refer to table 1 below).
Example 4.
In the LiPF process 6 Dissolving in non-aqueous organic solvent to obtain LiPF 6 A lithium secondary battery was prepared in the same manner as in example 1, except that a nonaqueous electrolytic solution was prepared by adding 11.0 wt% of the compound represented by formula 1a and 0.5 wt% of VEC, 1.0 wt% of PS, 5.0 wt% of FEC, 1.0 wt% of SN, and 0.5 wt% of LiODFB as other additives (refer to table 1 below).
Example 5.
In the LiPF process 6 Dissolved in the non-solventIn an aqueous organic solvent to give LiPF 6 A lithium secondary battery was prepared in the same manner as in example 1, except that a nonaqueous electrolytic solution was prepared by adding 1.0 wt% of the compound represented by formula 1b and 0.5 wt% of VEC, 1.0 wt% of PS, 5.0 wt% of FEC, 1.0 wt% of SN, and 0.5 wt% of LiODFB as other additives (refer to table 1 below).
Example 6.
In the LiPF process 6 Dissolving in non-aqueous organic solvent to obtain LiPF 6 A lithium secondary battery was prepared in the same manner as in example 1, except that a nonaqueous electrolytic solution was prepared by adding 1.0 wt% of the compound represented by formula 1c and 0.5 wt% of VEC, 1.0 wt% of PS, 5.0 wt% of FEC, 1.0 wt% of SN, and 0.5 wt% of LiODFB as other additives (refer to table 1 below).
Comparative example 1.
In the LiPF process 6 Dissolving in non-aqueous organic solvent to obtain LiPF 6 A lithium secondary battery was prepared in the same manner as in example 1, except that a nonaqueous electrolyte was prepared by adding 0.5 wt% VEC, 1.0 wt% PS, 5.0 wt% FEC, 1.0 wt% SN, and 0.5 wt% LiODFB as other additives (refer to table 1 below).
Comparative example 2.
A lithium secondary battery was prepared in the same manner as in example 1, except that a compound represented by the following formula 2 was added instead of the compound represented by formula 1a to prepare a nonaqueous electrolytic solution (refer to table 1 below).
[ 2]
Comparative example 3.
A lithium secondary battery was prepared in the same manner as in example 2, except that a compound represented by the following formula 2 was added instead of the compound represented by formula 1a to prepare a nonaqueous electrolytic solution (refer to table 1 below).
TABLE 1
Meanwhile, in table 1, abbreviations of each compound have the following meanings.
EC: ethylene carbonate
PC: propylene carbonate
EP: propionic acid ethyl ester
PP: propionic acid propyl ester
Experimental example
Experimental example 1: interface resistance assessment
After the lithium secondary batteries prepared in examples 1 to 6 and the lithium secondary batteries prepared in comparative examples 1 to 3 were discharged at room temperature (25 ℃) at a rate of 5C for 10 seconds to adjust the SOC to 50%, initial interface resistances were calculated according to the amount of voltage drop measured using VMP3 (manufactured by Biologics), and the results were expressed as a contrast ratio (%) with respect to the secondary battery of comparative example 1, as shown in table 2 below.
Experimental example 2: room temperature discharge capacity
The lithium secondary batteries prepared in examples 1 to 3, 5 and 6 and the lithium secondary batteries prepared in comparative examples 1 to 3 were subjected to constant current to 4.45V in CC-CV (constant current constant voltage) mode at room temperature (25 ℃) at a rate of 0.2C, and then the current was controlled at 4.45V in a constant voltage manner. Table 2 below lists the capacities measured using PNE-0506 charge and discharge devices (manufacturer: PNE Solution,5V, 6A) obtained at a rate of 0.2C in CC (constant current) by a cutoff voltage of 3.0V during discharge.
Experimental example 3: room temperature capacity retention rate
The lithium secondary batteries prepared in examples 1 to 6 and the lithium secondary batteries prepared in comparative examples 1 to 3 were charged to 4.45V at a constant current/constant voltage condition of 25 ℃ at a rate of 2C and discharged to 3.0V at a constant current condition at a rate of 1C, and as one cycle, the discharge capacity and resistance after 1 cycle were measured using a PNE-0506 charge-discharge device (manufacturer: PNE solution,5V,6 a).
Subsequently, after 200 charge and discharge cycles were performed under the same cycle conditions as described above, the capacity retention (%) was calculated by using the following equation 1, and the results are shown in the following table 2.
[ equation 1]
Capacity retention (%) = (discharge capacity after 200 cycles/discharge capacity after 1 cycle) ×100
TABLE 2
Referring to table 2 above, it can be understood that the secondary batteries of examples 1 to 3, 5 and 6 of the present application were improved in interfacial resistance (%), discharge capacity (mAh) and capacity retention (%) after 200 cycles at room temperature (25 ℃) as compared with the secondary batteries of comparative examples 1 to 3.
Meanwhile, it appears that in the case of the secondary battery of example 4 containing a considerable amount of additive, interfacial resistance (%) is increased and capacity retention (%) is relatively decreased due to an increase in resistance and an increase in side reaction caused by the additive inside the battery, as compared with the secondary batteries of examples 1 to 3, 5 and 6.
Experimental example 4: low temperature discharge capacity
The current was controlled at 4.45V in a constant voltage manner after constant current was applied to the lithium secondary batteries prepared in examples 1 to 6 and the lithium secondary batteries prepared in comparative examples 1 to 3 at a constant current-constant voltage manner at a constant current-constant voltage ratio of 0.2C at a low temperature (10 ℃). Then, the lithium secondary battery was cut off discharged at 3.0V in a CC (constant current) manner at a rate of 0.2C, and the discharge capacity was measured using PNE-0506 charge-discharge apparatus (manufacturer: PNE Solution,5V, 6A). The results are shown in Table 3 below.
TABLE 3
| Low temperature (10 ℃) discharge capacity (mAh) | |
| Example 1 | 4689 |
| Example 2 | 4701 |
| Example 3 | 4667 |
| Example 4 | 4235 |
| Example 5 | 4721 |
| Example 6 | 4691 |
| Comparative example 1 | 4214 |
| Comparative example 2 | 4146 |
| Comparative example 3 | 4068 |
Referring to table 3 above, it can be understood that the secondary batteries of examples 1 to 6 have discharge capacities of 4235mAh or more at low temperatures, and have improved discharge capacities as compared with the secondary batteries of comparative examples 1 to 3.
Experimental example 5:2C charging potential
When the secondary batteries prepared in examples 1 to 3, 5 and 6 of the present application and the secondary batteries prepared in comparative examples 1 to 3 were charged in CC-CV mode at a 2C rate at a low temperature (10 ℃), the capacity of the initial charge stage (-SOC 20%) was measured using a PNE-0506 charge-discharge device (manufacturer: PNE Solution,5v,6 a), and the 2C charge potential (average voltage) of the initial charge stage was calculated using the following equation 2, and the results are shown in table 4 below.
[ equation 2]
2C charge potential (average voltage) (V) =charge energy (mWh)/(capacity of SOC 20% (mAh)) to reach SOC 20%
TABLE 4
| 2C charging potential (V) at low temperature (10 ℃ C.) | |
| Example 1 | 4.08 |
| Example 2 | 4.02 |
| Example 3 | 4.10 |
| Example 5 | 4.02 |
| Example 6 | 4.08 |
| Comparative example 1 | 4.23 |
| Comparative example 2 | 4.25 |
| Comparative example 3 | 4.29 |
Referring to table 4 above, it can be understood that the secondary batteries of examples 1 to 3, 5 and 6 have a 2C charge potential of 4.10V or less at low temperature and can be charged at a lower potential than the secondary batteries of comparative examples 1 to 3.
It can be understood that in the case of the secondary battery of example 2, the 2C charge potential was lower, which means that the overpotential was decreased, as compared with the secondary battery of example 1. Therefore, it is understood that the effect of lowering the resistance is significantly improved when the additive content is 1.0 wt% as compared to 0.1 wt% of the additive content.
On the other hand, in the case of the secondary battery of example 3 having an additive content of 5.0 wt%, the film thickness increased, resulting in a relatively higher resistance, as compared with the secondary batteries of examples 1 and 2, whereby the potential was instead increased.
Referring to table 4 above, it can be understood that in the case of the secondary battery of example 1 having an additive content of 0.1 wt%, the fluorocarbon component in the SEI component is relatively low, and thus its effect of reducing resistance is relatively reduced compared to the secondary battery of example 2 having an additive content of 1.0 wt%. That is, it is confirmed that the resistance of the SEI film decreases as the content of fluorocarbon components contributing to Li diffusion increases due to lower surface energy during the formation of the SEI film.
Claims (9)
1. A nonaqueous electrolyte for a lithium secondary battery, comprising:
a lithium salt of the metal salt,
a non-aqueous organic solvent, and
a compound represented by formula 1:
[ 1]
Wherein, in the formula 1,
R 1 and R is 2 Each independently is an alkylene group having 1 to 10 carbon atoms, and
R 3 is an alkyl group having 1 to 20 carbon atoms substituted with one or more fluorine atoms.
2. The nonaqueous electrolyte for lithium secondary battery according to claim 1, wherein in formula 1, R 1 And R is 2 Each independently is an alkylene group having 1 to 5 carbon atoms, R 3 Is an alkyl group having 3 to 20 carbon atoms substituted with one or more fluorine atoms.
3. The nonaqueous electrolyte for lithium secondary battery according to claim 1, wherein in formula 1, R 1 And R is 2 Each independently is an alkylene group having 1 to 3 carbon atoms, R 3 Is an alkyl group having 3 to 15 carbon atoms substituted with one or more fluorine atoms.
4. The nonaqueous electrolyte for lithium secondary battery according to claim 1, wherein, in the compound represented by formula 1, R 3 Is an alkyl group having 3 to 10 carbon atoms substituted with one or more fluorine atoms.
5. The nonaqueous electrolyte for lithium secondary batteries according to claim 1, wherein the compound represented by formula 1 may be at least one of compounds represented by the following formulas 1a to 1 c:
[ 1a ]
[ 1b ]
[ 1c ]
6. The nonaqueous electrolytic solution for lithium secondary battery according to claim 1, wherein the compound represented by formula 1 is present in an amount of 0.01 to 10.0% by weight based on the total weight of the nonaqueous electrolytic solution for lithium secondary battery.
7. The nonaqueous electrolytic solution for lithium secondary battery according to claim 1, wherein the compound represented by formula 1 is present in an amount of 0.1 to 6.0% by weight based on the total weight of the nonaqueous electrolytic solution for lithium secondary battery.
8. The nonaqueous electrolyte for lithium secondary batteries according to claim 1, wherein the nonaqueous electrolyte for lithium secondary batteries further comprises at least one selected from the group consisting of: halogen substituted or unsubstituted carbonate compounds, sultone compounds, sulfate compounds, phosphate compounds or phosphite compounds, borate compounds, nitrile compounds, amine compounds, silane compounds and lithium compounds.
9. A lithium secondary battery, comprising:
a positive electrode including a positive electrode active material;
a negative electrode including a negative electrode active material;
a separator disposed between the negative electrode and the positive electrode; and the nonaqueous electrolyte for lithium secondary batteries according to claim 1.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2021-0135188 | 2021-10-12 | ||
| KR10-2022-0127418 | 2022-10-05 | ||
| KR1020220127418A KR102522492B1 (en) | 2021-10-12 | 2022-10-05 | Non-aqueous electrolyte for secondary battery and secondary battery comprising same |
| PCT/KR2022/015051 WO2023063648A1 (en) | 2021-10-12 | 2022-10-06 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116941088A true CN116941088A (en) | 2023-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280018013.4A Pending CN116941088A (en) | 2021-10-12 | 2022-10-06 | Nonaqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
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| Country | Link |
|---|---|
| CN (1) | CN116941088A (en) |
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2022
- 2022-10-06 CN CN202280018013.4A patent/CN116941088A/en active Pending
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