Non Aqueous Electrolyte Solution For Lithium Secondary Battery And Lithium Secondary Battery Comprising Same
Abstract:
The present invention relates to a non-aqueous electrolyte solution to which a Lewis base compound is added. The non-aqueous electrolyte solution can maintain the passivation ability of an SEI film when stored at high temperatures, by scavenging HF and PF5, which are formed as decomposition products of a lithium salt (LiPF6). In addition, the solution improvise the dissolution of a positive electrode and the self-discharge phenomenon of a negative electrode due to destruction of the SEI film, thereby enabling the manufacture of a lithium secondary battery having improved battery performance. Moreover, the solution suppresses the additional decomposition of an electrolyte by forming an excellent initial film, and thus can provide a secondary battery having improved initial efficiency.
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Notices, Deadlines & Correspondence
Tower 1, 108, Yeoui-daero,
Yeongdeungpo-gu,
Seoul 07335
Inventors
1. KIM, Hyun-Seung
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
2. AN, Yu-Ha
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
3. OH, Jeong-Woo
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
4. LEE, Chul-Haeng
LG Chem Research Park, 188, Munji-ro,
Yuseong-gu,
Daejeon 34122
Specification
Specification
Title of Invention: Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same
technical field
[One]
This application claims priority based on Korean Patent Application No. 10-2020-0021885 filed on February 21, 2020. The present invention relates to a non-aqueous electrolyte for a lithium secondary battery comprising a non-aqueous electrolyte additive having an excellent initial film-forming effect while having an excellent effect of removing decomposition products generated from lithium salts, and a lithium secondary battery having improved initial battery efficiency and self-discharge characteristics by including the same it's about
[2]
background
[3]
As personal IT devices and computer networks are developed due to the development of the information society, and the overall society's dependence on electric energy increases accordingly, technology development for efficiently storing and utilizing electric energy is required.
[4]
Among the technologies developed for this purpose, the most suitable technology for various uses is a secondary battery-based technology. In the case of secondary batteries, interest in this is emerging because they can be miniaturized enough to be applied to personal IT devices, and can also be applied to electric vehicles and power storage devices. Among these secondary battery technologies, a lithium ion battery, which is a battery system with the highest theoretical energy density, is in the spotlight and is currently being applied to various devices.
[5]
Lithium ion batteries do not directly apply lithium metal to the electrode, but instead have a positive electrode made of a transition metal oxide containing lithium, a negative electrode made of a carbon-based material such as graphite that can store lithium, and a medium that delivers lithium ions. It is composed of an electrolyte solution and a separator.
[6]
As the electrolyte is known as a component that has a great influence on the stability and safety of the battery, many studies are being conducted on this.
[7]
The electrolyte solution for a lithium ion battery is composed of a lithium salt, an organic solvent dissolving it, and a functional additive. In order to improve the electrochemical properties of the battery, proper selection of these components is important. Representative lithium salts currently used include LiPF 6 , LiBF 4 , LiFSI (lithium fluorosulfonyl imide, LiN(SO 2 F) 2 ), LiTFSI (lithium (bis)trifluoromethanesulfonyl imide, LiN(SO 2 CF 3 ) 2 ) or LiBOB ( lithium bis(oxalate) borate, LiB(C 2 O 4 ) 2 ), and the like, and the organic solvent is an ester-based organic solvent or an ether-based organic solvent.
[8]
On the other hand, the lithium ion battery has a disadvantage in that the performance deteriorates due to an increase in resistance and a decrease in capacity during charging/discharging or storage at a high temperature. At this time, one of the causes of this problem is a side reaction that occurs due to deterioration of the electrolyte at a high temperature, especially deterioration due to the decomposition of lithium salt. When the by-product of these salts decomposes the film formed on the surface of the anode and the cathode after activation, there is a problem of lowering the passivation ability of the film, thereby causing additional decomposition of the electrolyte and accompanying self-discharge. there is
[9]
Among the electrode materials of lithium ion batteries, especially in the case of negative electrodes, graphite-based negative electrodes are most often used. In the case of graphite, the operating potential is 0.3 V ( vs. Li/Li + ) or less, so the electrochemical lower than the electrochemical stability window. Therefore, the currently used electrolyte is first reduced and decomposed. This reduction-decomposed electrolyte product forms a solid electrolyte interphase (SEI) film that transmits lithium ions but inhibits further decomposition of the electrolyte.
[10]
However, if the SEI membrane does not have sufficient passivation ability to suppress further decomposition of the electrolyte, the electrolyte is further decomposed during storage and the charged graphite is self-discharged, and consequently, the potential of the battery is lowered.
[11]
For example, acids such as HF and PF 5 generated by thermal decomposition of LiPF 6 , a lithium salt widely used in lithium ion batteries, deteriorate the film or electrode surface. For this reason, when the electrode surface is deteriorated, transition metal elution occurs in the anode to increase resistance, and capacity may decrease due to loss of redox centers. Moreover, in the case of eluted metal ions, they are electrodeposited on the negative electrode and consume electrons due to metal electrodeposition and further electrolyte decomposition, thereby increasing irreversible capacity, which not only decreases cell capacity, but also increases resistance and may cause self-discharge of the graphite negative electrode. have.
[12]
Therefore, in order to suppress the damage of the SEI film at a recent high temperature and maintain the passivation ability, an electrolyte solution additive containing a functional group that can easily undergo reductive decomposition in the electrolyte solution is introduced, or a factor that can affect the passivation ability, for example For example, a method for removing decomposition products (HF, PF 5 , etc.) of lithium salts generated by heat or moisture has been proposed.
[13]
DETAILED DESCRIPTION OF THE INVENTION
technical challenge
[14]
An object of the present invention is to provide a non-aqueous electrolyte additive which is a Lewis base compound, which reacts rapidly with acid and is excellent in the effect of forming a SEI film and removing decomposition products generated inside the non-aqueous electrolyte, and a non-aqueous electrolyte for a lithium secondary battery comprising the same.
[15]
In addition, an object of the present invention is to provide a lithium secondary battery having improved initial efficiency and self-discharge characteristics by including the non-aqueous electrolyte additive and electrolyte.
[16]
means of solving the problem
[17]
The present invention relates to a non-aqueous electrolyte for a lithium secondary battery.
[18]
A first aspect of the present invention relates to the non-aqueous electrolyte, wherein the non-aqueous electrolyte includes a compound represented by the following [Formula 1] as a lithium salt, an organic solvent, and an additive.
[19]
[20]
[Formula 1]
[21]
[22]
[23]
In [Formula 1], Q is absent or is a substituted or unsubstituted C1 to C10 alkyl group, and A1, A2 and A3 are each independently hydrogen or a substituted or unsubstituted C1 to C10 alkyl group.
[24]
In a second aspect of the present invention, in the first aspect, Q is a chain or branched alkyl group, an alkenyl group, or an alkynyl group.
[25]
A third aspect of the present invention, according to the second aspect, wherein Q is at least one hydrogen is substituted with a halogen element selected from Cl, F, Br and I.
[26]
A fourth aspect of the present invention, in any one of the first to third aspects, the additive comprises a compound represented by the following [Formula 1a].
[27]
[28]
[Formula 1a]
[29]
[30]
[31]
In a fifth aspect of the present invention, in any one of the first to fourth aspects, the lithium salt comprises Li + as a cation, and F - , Cl - , Br - , I - , NO 3 as an anion. - , 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 O4 - , 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 - , PO 2 F 2 - , SCN - and (CF 3 CF 2 SO 2 ) It includes at least one selected from the group consisting of 2 N - .
[32]
In a sixth aspect of the present invention, in any one of the first to fifth aspects, the additive is included in an amount of 0.1 wt% to 2 wt%, based on 100 wt% of the non-aqueous electrolyte for a lithium secondary battery.
[33]
In a seventh aspect of the present invention, in any one of the first to sixth aspects, the additive is contained in an amount of 0.3 wt% to 1.5 wt%, based on 100 wt% of the non-aqueous electrolyte for a lithium secondary battery.
[34]
An eighth aspect of the present invention relates to a lithium secondary battery, wherein the battery includes a positive electrode, a negative electrode, a separator, and a non-aqueous electrolyte for a lithium secondary battery, wherein the non-aqueous electrolyte is according to any one of the first to seventh aspects.
[35]
Effects of the Invention
[36]
According to the present invention, by including a Lewis base compound as an electrolyte additive in the preparation of a non-aqueous electrolyte, HF and PF 5 formed as a decomposition product of a lithium salt (LiPF 6 ) mainly used in a non-aqueous electrolyte are removed (scavenging) and high temperature During storage, the passivation ability of the SEI membrane can be maintained. In addition, by including the non-aqueous electrolyte containing the Lewis base compound as an additive, the self-discharge phenomenon caused by elution of the positive electrode and the destruction of the SEI film of the negative electrode can be improved, and thus a lithium secondary battery with improved battery performance can be manufactured. In addition, it is possible to provide a secondary battery with improved initial efficiency by suppressing additional electrolyte decomposition by excellently forming the initial film.
[37]
Brief description of the drawing
[38]
The following drawings attached to the present specification illustrate preferred embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the above-described content of the present invention, so the present invention is limited to the matters described in those drawings It should not be construed as being limited.
[39]
1 is a graph showing a differential capacity curve according to Experimental Example 1 of Example 1 and Comparative Example 1 of the present invention.
[40]
2 is a result showing the initial efficiency during the activation process according to Experimental Example 2 of Example 1 and Comparative Example 1 of the present invention.
[41]
3 is a result showing the drop of the initial OCV (open-circuit-voltage) according to Experimental Example 3 of Example 1 and Comparative Example 1 of the present invention.
[42]
Modes for carrying out the invention
[43]
Hereinafter, the present invention will be described in more detail.
[44]
The terms or words used in the present specification and claims should not be construed as being limited to their ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.
[45]
In the lithium secondary battery, as the non-aqueous electrolyte is decomposed during initial charging and discharging, a film having a passivation ability is formed on the surfaces of the positive and negative electrodes to improve high-temperature storage characteristics. However, the film may be deteriorated by acids such as HF and PF 5 generated by thermal decomposition of anions such as LiPF 6 , a lithium salt widely used in lithium ion batteries . As a result of the acid attack, the elution of the transition metal element occurs in the anode, and the resistance of the electrode surface increases due to the structural change of the surface, and the theoretical capacity decreases as the metal elements, which are the redox centers, are lost, and thus the expression capacity may decrease. In addition, in the case of the eluted transition metal ions, they not only consume electrons by electrodeposition on the cathode reacting in the strong reduction potential band, but also destroy the SEI film when electrodeposited. Accordingly, as the surface of the anode is exposed, the resistance of the anode increases, causing an additional electrolyte decomposition reaction. As a result, there is a problem in that the capacity of the cell is continuously decreased while the irreversible capacity is increased.
[46]
[47]
Accordingly, in the present invention, by including a Lewis base compound as a non-aqueous electrolyte additive, acid caused by the decomposition of lithium salts is removed, thereby preventing deterioration of the SEI film or elution of transition metals from the positive electrode during high-temperature storage while preventing the active material surface An object of the present invention is to provide a non-aqueous electrolyte having excellent film-forming ability and a lithium secondary battery including the same.
[48]
[49]
Non-aqueous electrolyte for lithium secondary battery
[50]
Specifically, an embodiment of the present invention provides a non-aqueous electrolyte for a lithium secondary battery comprising a compound represented by the following [Formula 1] as a lithium salt, an organic solvent and an additive.
[51]
[52]
[Formula 1]
[53]
[54]
[55]
In [Formula 1], Q may be absent or a substituted or unsubstituted C 1 to C 10 alkyl group. In one embodiment of the present invention, Q may be a chain or branched alkyl group, an alkenyl group, or an alkynyl group. Meanwhile, in Q, at least one hydrogen may be substituted with a halogen element selected from Cl, F, Br, and I. Meanwhile, in one embodiment of the present invention, A1, A2, and A3 may each independently be hydrogen or a substituted or unsubstituted C1-C10 alkyl group.
[56]
[57]
(1) lithium salt
[58]
First, in the non-aqueous electrolyte for a lithium secondary battery according to an embodiment of the present invention, the lithium salt may be used without limitation, those commonly used in the preparation of an electrolyte for a lithium secondary battery, for example, Li + as a cation. , F - , Cl - , Br - , I - , NO 3 - , N(CN) 2 - , BF 4 - , ClO 4 - , AlO 4 - , AlCl 4 - , PF 6 - , SbF 6 - , PO 2 F 2 - 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 ) 2N - , 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 - and (CF 3 CF 2 SO 2 ) At least one selected from the group consisting of 2 N - may be mentioned. Specifically, the lithium salt is LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiAlO 4 , LiAlCl 4 , LiPF 6 , LiSbF 6 , LiAsF 6 , LiPO 2 F 2 , 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 ) ) may be at least one selected from the group consisting of 2. Specifically, the lithium salt is LiPO 2 F 2 , 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 may include a single substance or a mixture of two or more selected from the group consisting of.
[59]
The lithium salt may be appropriately changed within the range that can be used in general, but to be included in the electrolyte at a concentration of 0.8 M to 4.0 M, specifically, at a concentration of 1.0M to 3.0M, in order to obtain an optimal effect of forming a film for preventing corrosion of the electrode surface. can
[60]
If the concentration of the lithium salt is less than 0.8 M, the effect of improving the low-temperature output of the lithium secondary battery and improving the cycle characteristics during high-temperature storage is insignificant. can
[61]
[62]
(2) organic solvents
[63]
In the non-aqueous electrolyte for a lithium secondary battery according to the present specification, the organic solvent may include a cyclic carbonate-based organic solvent, a linear carbonate-based organic solvent, or a mixed organic solvent thereof.
[64]
The cyclic carbonate-based organic solvent is a high-viscosity organic solvent that has a high dielectric constant and can well dissociate lithium salts in the electrolyte, and specific examples thereof include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene. At least one organic solvent selected from the group consisting of carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and vinylene carbonate, among them, ethylene carbonate may include.
[65]
In addition, the linear carbonate-based organic solvent is an organic solvent having a low viscosity and a low dielectric constant, and representative examples thereof include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate ( EMC), at least one organic solvent selected from the group consisting of methyl propyl carbonate and ethyl propyl carbonate may be used, and specifically, ethyl methyl carbonate (EMC) may be included.
[66]
In addition, the organic solvent is a linear ester-based organic solvent and a cyclic ester in at least one carbonate-based organic solvent selected from the group consisting of the cyclic carbonate-based organic solvent and the linear carbonate-based organic solvent in order to prepare an electrolyte having high ionic conductivity. It may further include at least one or more ester-based organic solvents selected from the group consisting of organic solvents.
[67]
Specific examples of the linear ester-based organic solvent include at least one organic solvent selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate and butyl propionate. can be heard
[68]
In addition, as the cyclic ester-based organic solvent, at least one organic solvent selected from the group consisting of γ-butyrolactone, γ-valerolactone, γ-caprolactone, σ-valerolactone, ε-caprolactone, can be heard
[69]
Meanwhile, as the organic solvent, an organic solvent commonly used in an electrolyte for a lithium secondary battery may be added without limitation, if necessary. For example, at least one organic solvent of an ether-based organic solvent, an amide-based organic solvent, and a nitrile-based organic solvent may be further included.
[70]
[71]
(3) additives
[72]
The non-aqueous electrolyte for a lithium secondary battery of the present invention may include a compound represented by the following [Formula 1] as an additive.
[73]
[74]
[Formula 1]
[75]
[76]
[77]
In Formula 1, Q may be absent or may be a substituted or unsubstituted C 1 to C 10 alkyl group. In an embodiment of the present invention, Q may be a chain or branched alkyl group, an alkenyl group, or an alkynyl group. Meanwhile, in one embodiment of the present invention, in Q, at least one hydrogen may be substituted with a halogen element selected from Cl, F, Br, and I. Meanwhile, in one embodiment of the present invention, A1, A2, and A3 may each independently be hydrogen or a substituted or unsubstituted C1-C10 alkyl group.
[78]
[79]
The compound represented by Formula 1 may be a compound represented by Formula 1a as a representative example.
[80]
[81]
[Formula 1a]
[82]
[83]
[84]
In one embodiment of the present invention, the compound represented by Formula 1 may be included in an amount of 0.1 wt% to 2 wt% based on the total weight of the non-aqueous electrolyte. For example, it may include 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or 0.5 wt% or more within the above range. In addition, it may be included in the range of 1.7 wt% or less, 1.5 wt% or less, or 1.2 wt% or less within the above range. In Formula 1a, carbon in the cyclic compound is to which hydrogen (H) is bonded, and the existence of such hydrogen is apparent to those skilled in the art.
[85]
[86]
When the compound represented by Formula 1 is included in the above range, it is possible to manufacture a secondary battery with improved overall performance. For example, if the content of the compound represented by Formula 1 is less than 0.1 wt%, HF or PF 5 may be initially removed, but as time passes, the removal effect becomes insignificant and the initial SEI formation effect by the additive is significantly reduced. can In addition, when the content of the compound represented by Formula 1 exceeds 2.0 wt%, side reactions and by-products due to excess additives may occur, thereby increasing the resistance of the secondary battery during high-temperature storage.
[87]
[88]
Therefore, when the content of the compound represented by Formula 1 is 0.1 wt% or more to 2 wt% or less, specifically 0.1 wt% to 1.7 wt%, more specifically 0.3 wt% to 1.5 wt% Acids such as HF and PF 5 , which are decomposition products of lithium salts, can be more effectively removed while minimizing disadvantages such as side reactions, capacity reduction, and resistance increase .
[89]
[90]
Since the compound represented by Formula 1 included as an electrolyte additive in the present specification is a Lewis base-based compound including an imidazole functional group, by-products that cause battery deterioration at high temperatures, for example, due to decomposition of lithium salts The generated Lewis acid (eg HF or PF 5 ) can be easily scavenged. As a result, it is possible to suppress the deterioration behavior due to the chemical reaction of the surface film of the anode or cathode caused by Lewis acid, so it is possible to prevent further decomposition of the electrolyte solution of the battery due to the destruction of the film, and furthermore, it is possible to alleviate the self-discharge of the secondary battery. High-temperature storage characteristics can be improved. In addition, the compound contains a C = O functional group, so it has excellent solubility in a solvent group generally used in lithium ion batteries, and can easily bind with a Li salt, thereby protecting the surface of the anode during reductive decomposition. - The ability to form SEI, an organic/inorganic complex, is also excellent.
[91]
[92]
(4) additional additives
[93]
In addition, the non-aqueous electrolyte for a lithium secondary battery of the present invention prevents the anode from decaying due to decomposition of the non-aqueous electrolyte in a high-output environment, or has low-temperature high-rate discharge characteristics, high-temperature stability, overcharge prevention, and battery expansion inhibition effect at high temperature. In order to improve it, additional additives may be further included in the non-aqueous electrolyte if necessary.
[94]
[95]
Representative examples of these additional additives include a cyclic carbonate-based compound, a halogen-substituted carbonate-based compound, a sultone-based compound, a sulfate-based compound, a phosphate-based compound, a borate-based compound, a nitrile-based compound, a benzene-based compound, an amine-based compound, and a silane-based compound At least one additional additive selected from the group consisting of compounds and lithium salt-based compounds may be included.
[96]
The cyclic carbonate-based compound may be vinylene carbonate (VC) or vinylethylene carbonate. The halogen-substituted carbonate-based compound may include fluoroethylene carbonate (FEC)).
[97]
The sultone-based compound includes 1,3-propane sultone (PS), 1,4-butane sultone, ethenesultone, 1,3-propene sultone (PRS), 1,4-butene sultone, and 1-methyl-1,3 - at least one compound selected from the group consisting of propene sultone.
[98]
The sulfate-based compound may include ethylene sulfate (Esa), trimethylene sulfate (TMS), or methyl trimethylene sulfate (MTMS).
[99]
The phosphate-based compound is lithium difluoro (bisoxalato) phosphate, lithium difluorophosphate (LiPO 2 F 2 ), tetramethyl trimethyl silyl phosphate, trimethyl silyl phosphite, tris (2,2,2-trifluoro and at least one compound selected from the group consisting of roethyl)phosphate and tris(trifluoroethyl)phosphite.
[100]
The borate-based compound may include tetraphenylborate and lithium oxalyldifluoroborate.
[101]
The nitrile-based compound is succinonitrile, adiponitrile, acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzo Nitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, and 4-fluorophenylacetonitrile, Propargyl 1H-imidazole-1-carboxylate At least one compound selected from the group consisting of may be mentioned.
[102]
The benzene-based compound may include fluorobenzene, the amine-based compound may include triethanolamine or ethylenediamine, and the silane-based compound may include tetravinylsilane.
[103]
[104]
The lithium salt-based compound is a compound different from the lithium salt included in the non-aqueous electrolyte, and is selected from the group consisting of LiPO 2 F 2 , LiODFB, LiBOB (lithium bisoxalatoborate (LiB(C 2 O 4 ) 2 ) and LiBF 4 ). one or more compounds.
[105]
[106]
Among these additional additives, when vinylene carbonate, vinylethylene carbonate, or succinonitrile is included, a more robust SEI film may be formed on the surface of the anode during the initial activation process of the secondary battery.
[107]
[108]
When the LiBF 4 is included, generation of a gas that may be generated due to the decomposition of the electrolyte during storage at a high temperature is suppressed, thereby improving the high-temperature stability of the secondary battery.
[109]
Meanwhile, two or more of the additional additives may be mixed and used, and may be included in an amount of 0.01 to 50% by weight, specifically 0.01 to 20% by weight, based on the total weight of the non-aqueous electrolyte. When the content of the additional additive is less than 0.01% by weight, the effect of improving the low-temperature output and high-temperature storage and high-temperature life characteristics of the battery is insignificant, and when the content of the additional additive exceeds 50% by weight, the excess additive is Therefore, there is a possibility that side reactions may occur excessively during charging and discharging of the battery. In particular, when the additives for forming the SEI film are added in excess, they may not be sufficiently decomposed at a high temperature, so that unreacted substances may be generated or deposited in the electrolyte at room temperature. Accordingly, a side reaction in which the life or resistance characteristic of the secondary battery is deteriorated may occur.
[110]
[111]
lithium secondary battery
[112]
Further, in another embodiment of the present invention, there is provided a lithium secondary battery including the non-aqueous electrolyte for a lithium secondary battery of the present invention.
[113]
[114]
On the other hand, the lithium secondary battery of the present invention can be manufactured by forming an electrode assembly in which a positive electrode, a negative electrode, and a separator are sequentially stacked between the positive and negative electrodes, stored in a battery case, and then adding the non-aqueous electrolyte of the present invention.
[115]
The method for manufacturing the lithium secondary battery of the present invention may be manufactured and applied according to a conventional method known in the art, and will be described in detail below.
[116]
[117]
(1) Anode
[118]
The positive electrode may be prepared by coating a positive electrode slurry including a positive electrode active material, a binder, a conductive material, and a solvent on a positive electrode current collector, followed by drying and rolling.
[119]
The positive electrode current collector is not particularly limited as long as it has conductivity without causing a chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. , nickel, titanium, silver or the like surface-treated may be used.
[120]
The positive active material is a compound capable of reversible intercalation and deintercalation of lithium, and specifically, may include a lithium composite metal oxide including lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide is a lithium-manganese oxide (eg, LiMnO 2 , LiMn 2 O 4 , etc.), a lithium-cobalt-based oxide (eg, LiCoO 2 , etc.), lithium-nickel-based oxide (eg, LiNiO 2 , etc.), lithium-nickel-manganese oxide (eg, LiNi 1-Y Mn Y O 2 (0
Documents
Application Documents
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Name
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202217030485.pdf
2022-05-27
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202217030485-TRANSLATIOIN OF PRIOIRTY DOCUMENTS ETC. [27-05-2022(online)].pdf
2022-05-27
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202217030485-STATEMENT OF UNDERTAKING (FORM 3) [27-05-2022(online)].pdf
2022-05-27
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202217030485-PROOF OF RIGHT [27-05-2022(online)].pdf