WO2019009595A1 - Additif d'électrolyte et solution d'électrolyte non-aqueux pour accumulateur au lithium le contenant - Google Patents

Additif d'électrolyte et solution d'électrolyte non-aqueux pour accumulateur au lithium le contenant Download PDF

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WO2019009595A1
WO2019009595A1 PCT/KR2018/007530 KR2018007530W WO2019009595A1 WO 2019009595 A1 WO2019009595 A1 WO 2019009595A1 KR 2018007530 W KR2018007530 W KR 2018007530W WO 2019009595 A1 WO2019009595 A1 WO 2019009595A1
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Prior art keywords
lithium
additive
group
compound
carbon atoms
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PCT/KR2018/007530
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English (en)
Korean (ko)
Inventor
임영민
이철행
이경미
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주식회사 엘지화학
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Priority claimed from KR1020180076420A external-priority patent/KR102477644B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880003987.9A priority Critical patent/CN109891654B/zh
Priority to JP2019528062A priority patent/JP7034404B2/ja
Priority to PL18828080.4T priority patent/PL3512028T3/pl
Priority to ES18828080T priority patent/ES2929134T3/es
Priority to EP18828080.4A priority patent/EP3512028B1/fr
Priority to US16/339,537 priority patent/US11063296B2/en
Publication of WO2019009595A1 publication Critical patent/WO2019009595A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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

Definitions

  • the present invention relates to an electrolyte additive capable of improving the performance of a battery and a nonaqueous electrolyte solution for a lithium secondary battery comprising the electrolyte additive.
  • the secondary battery examples include a nickel-cadmium battery, a nickel-metal hydride battery, a nickel-hydrogen battery, and a lithium secondary battery.
  • the secondary battery exhibits a discharge voltage two times higher than that of a conventional battery using an aqueous alkaline solution.
  • studies have been made on a lithium secondary battery which has a high energy density per unit weight and can be rapidly charged.
  • a positive electrode or a negative electrode active material is applied to a current collector with an appropriate thickness and length, or the active material itself is coated in a film form and wound or laminated with a separator as an insulator to form an electrode group. , And an electrolyte is injected. At this time, lithium metal oxide is used as the cathode active material, and lithium metal, lithium alloy, crystalline or amorphous carbon or carbon composite is used as the anode active material.
  • the lithium secondary battery is charged and discharged while repeating a process in which lithium ions are intercalated and deintercalated from the lithium metal oxide in the positive electrode to the graphite electrode in the negative electrode.
  • lithium since lithium is highly reactive, it reacts with the carbon electrode to form Li 2 CO 3 , LiO, LiOH and the like to form a film on the surface of the cathode.
  • This film is called Solid Electrolyte Interface (SEI) film.
  • SEI film formed at the beginning of charging prevents the reaction between lithium ion and carbon anode or other materials during charging and discharging. It also acts as an ion tunnel, allowing only lithium ions to pass through.
  • the ion tunnel serves to prevent the collapse of the structure of the carbon anode by co-intercalating the organic solvent of the electrolyte having a large molecular weight, which is solvated by lithium ion and co-migrated together with the carbon anode.
  • a solid SEI film must always be formed on the cathode of the lithium secondary battery.
  • a compound that can be used as an electrolyte additive for improving the overall performance of the battery such as a power SEI film formed on the anode and the cathode to improve the output characteristics, high temperature storage characteristics, and lifetime characteristics.
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a novel electrolyte additive for improving overall performance such as output, capacity, cycle characteristics and storage characteristics of a lithium secondary battery.
  • the present invention also provides a non-aqueous electrolyte solution for a lithium secondary battery comprising a lithium salt, an organic solvent, and the electrolyte additive.
  • the present invention also provides a lithium secondary battery comprising the non-aqueous electrolyte for the lithium secondary battery.
  • the present invention provides an electrolyte additive comprising a compound represented by the following general formula (1).
  • X 1 and X 2 are P, Y 1 to Y 4 are each independently O or S, L is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 to R 4 are each independently hydrogen , A halogen atom, a nitrile group, or a monovalent hydrocarbon group of 1 to 20 carbon atoms, wherein the divalent hydrocarbon group of 1 to 10 carbon atoms and the monovalent hydrocarbon group of 1 to 20 carbon atoms are substituted or unsubstituted, At least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • L is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms
  • each of R 1 to R 4 is independently a halogen atom or a substituted or unsubstituted C1- A monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • the compound of formula (1) may be selected from compounds represented by the following formula (1a) or (1b).
  • the first additive may be included in an amount of about 0.1 wt% to 6 wt%, specifically 0.5 wt% to 5 wt% based on the total weight of the nonaqueous electrolyte solution.
  • the nonaqueous electrolyte solution may further include a second additive selected from the group consisting of a non-lithium type additive, a lithium type additive, and a mixture thereof.
  • the non-lithium type additive may be at least one selected from the group consisting of a carbonate compound, a phosphate compound, a borate compound, a silane compound, a sulfur compound, a nitrile compound and a benzene compound.
  • the non-lithium type additive may be included in an amount of about 0.01 wt% to 10 wt% based on the total weight of the non-aqueous electrolyte.
  • the lithium-based additive may be at least one selected from the group consisting of boron halide-based lithium, boron oxalate-based lithium, imidazole-based lithium, phosphate-based lithium, and sulfate-based lithium.
  • the lithium type additive may be contained in an amount of about 0.01% by weight to 10% by weight based on the total weight of the non-aqueous electrolyte.
  • a nonaqueous electrolyte solution containing a compound capable of maintaining a passive effect by increasing the effect of forming a stable SEI film on the surfaces of the positive electrode and the negative electrode, as an electrolyte additive it is possible to manufacture a lithium secondary battery having improved overall performance such as cycle capacity characteristics and high temperature storage characteristics.
  • the functional group may include " a " to " b " carbon atoms.
  • the "alkylene group having 1 to 5 carbon atoms” means an alkylene group containing from 1 to 5 carbon atoms, that is, -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, - CH 2 (CH 2 ) CH-, -CH (CH 2 ) CH 2 -, and -CH (CH 2 ) CH 2 CH 2 -.
  • substituted means that at least one hydrogen bonded to the carbon is replaced with an element other than hydrogen.
  • an alkyl group having 1 to 20 carbon atoms an alkyl group having 2 to 20 carbon atoms
  • novel electrolyte additives are provided.
  • the electrolyte additive may include a compound represented by the following general formula (1).
  • X 1 and X 2 are P, Y 1 to Y 4 are each independently O or S, L is a direct bond or a divalent hydrocarbon group having 1 to 10 carbon atoms, R 1 to R 4 are each independently hydrogen , A halogen atom, a nitrile group, or a monovalent hydrocarbon group of 1 to 20 carbon atoms, wherein the divalent hydrocarbon group of 1 to 10 carbon atoms and the monovalent hydrocarbon group of 1 to 20 carbon atoms are substituted or unsubstituted, At least one substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
  • L as a linking group may be a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.
  • R 1 to R 4 each independently represent a halogen atom or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a halogen atom, Fluorine (F).
  • a diether bond or a dithioether bond may be present depending on the structure of Y 3 and Y 4 . .
  • the compound of formula (1) as described above may be selected from compounds represented by the following formulas (1a) or (1b).
  • the compound of Formula 1 included as an electrolyte additive includes a difluorophosphate structure, so that a uniform thin film can be formed on the anode and the cathode instead of being decomposed on the surface of the anode. That is, oxygen of the difluorophosphate structure is adsorbed on the surface of the cathode where oxygen is lost, so that a thin film is formed to stabilize the surface of the anode and prevent exposure to the non-aqueous electrolyte. As a result, it is possible to suppress the generation of O 2 from the anode and the side reaction between the anode and the electrolyte, thereby improving the durability of the battery. In addition, since the difluorophosphate structure is reduced when the battery is driven, a durable and stable SEI film can be formed on the surface of the negative electrode, thereby improving durability and high-temperature storage characteristics of the battery.
  • a nonaqueous electrolyte solution for a lithium secondary battery comprising a lithium salt, an organic solvent, and an electrolyte additive of the present invention as a first additive may be provided.
  • the compound represented by the general formula (1) contained in the first additive is stable and does not decompose even at a high temperature, it does not cause side reactions such as decomposition on the surface of the anode or oxidation of the nonaqueous electrolyte. So that the effect of reversible capacity increase can be seen.
  • the first additive the compound of Formula 1
  • the first additive may be used in an amount of about 0.1% by weight to about 6% by weight based on the total weight of the nonaqueous electrolyte solution, specifically 0.5% by weight to 5% by weight, % ≪ / RTI > to 5% by weight.
  • the content of the first additive of Formula 1 is 0.1 wt% to 6 wt%, it is possible to form a solid SEI film on the surfaces of the positive and negative electrodes and to prevent the increase in resistance due to excessive film formation on the electrode surface during initial charging can do. If the content of the first additive exceeds 6% by weight, side reactions may occur due to excessive additives, thereby degrading the cycle life characteristics and the capacity characteristics of the battery. If the content of the first additive is less than 0.1% by weight The effect of charging the first additive is insignificant, and it may be difficult to form a stable SEI film.
  • the nonaqueous electrolyte solution for a lithium secondary battery of the present invention may further comprise a second additive capable of assisting the formation of a negative electrode coating as an auxiliary agent in the nonaqueous electrolyte, together with the first additive, the compound of Formula 1.
  • the kind of the second additive is not particularly limited, but may specifically include a lithium type additive and / or a non-lithium type additive.
  • the non-aqueous electrolyte solution for a lithium secondary battery of the present invention is more stable on the surfaces of the positive electrode and the negative electrode by mixing the non-lithium type additive and / or the non-lithium type additive together with the first additive, A solid SEI film can be formed, and overall performance improvement such as high-temperature storage characteristics and lifetime characteristics of the lithium secondary battery can be achieved.
  • non-lithium type additives and lithium type additives used as the second additive are as follows.
  • the non-lithium type additive is used in combination with the compound of Formula 1 to improve the performance of the lithium secondary battery.
  • the non-lithium type additive has an effect of expressing the compound of Formula 1, And can serve as a complementary agent for improving the mobility of lithium ions.
  • the content of the non-lithium type additive relative to the compound represented by the general formula (1) is not particularly limited, but when it is included in the non-aqueous electrolyte, it includes about 0.01 to 10% by weight based on the total weight of the non- And specifically may be used in an amount of 0.05 wt% to 10 wt%, more specifically 0.1 wt% to 8 wt%, and more specifically 0.1 wt% to 5 wt%. If the amount of the non-lithium type additive is less than 0.01% by weight, the effect of charging the non-lithium type additive is insignificant. If the amount of the non-lithium type additive is more than 10% by weight, May be deteriorated.
  • the non-lithium type additive may be at least one selected from a carbonate compound, a phosphate compound, a borate compound, a silane compound, a sulfur compound, a nitrile compound and a benzene compound.
  • vinylene carbonate vinylene carbonate, fluoroethylene carbonate (FEC), difluoroethylene carbonate or vinylethylene carbonate
  • FEC fluoroethylene carbonate
  • vinylethylene carbonate vinylethylene carbonate
  • the substituent such as an alkyl group having 1 to 3 carbon atoms is substituted .
  • the carbonate compound can mainly form an SEI film on the surface of the anode at the time of battery activation. Therefore, by using the carbonate compound in combination with the compound represented by the formula (1) forming the SEI film on the cathode, a stable SEI film is formed even at a high temperature, Improvement can be achieved.
  • the phosphate compound may be represented, for example, by the following formula (2).
  • a 1 to A 3 each independently represent -Si (R a ) n (R b ) 3-n or a propinyl group (-C ⁇ C), wherein R a and R b each independently represent a C 1-4 And n is an integer of 0 to 3;
  • the phosphate compound examples include a phosphate compound such as tris (trimethylsilyl) phosphate, tris (triethylsilyl) phosphate, tris (tripropylsilyl) phosphate, bis (trimethylsilyl) (triethylsilyl) phosphate, bis (Trimethylsilyl) phosphate, bis (tripropylsilyl) (trimethylsilyl) phosphate, bis (tridimethylsilyl) (tripropylsilyl) phosphate and the like can be applied.
  • the alkyl groups of the respective silyl groups may be different from each other.
  • the above phosphate-based compounds may be applied with dipropyl ethyl phosphate, diethyl propyl phosphate or the like.
  • the phosphate compound stabilizes PF 6 anions and the like in the electrolyte and helps form a positive electrode and a negative electrode film, the durability of the battery can be improved by being mixed with the compound represented by the formula (1).
  • the borate compound may be represented by the following formula (3).
  • a 4 to A 6 each independently represent -Si (R c ) m (R d ) 3-m or a propinyl group (-C? C), wherein R c and R d each independently represent a C 1-4 And m is an integer of 0 to 3.
  • a silyl group or a propynyl group such as the above-described phosphate-based compound may be bonded, and the silyl group and the propynyl group may have the same substituent as exemplified in the phosphate-based compound.
  • the borate compound promotes ion-pair separation of the lithium salt, improves the mobility of lithium ions, can lower the interfacial resistance of the SEI film, and can be used for a material such as LiF By dissociation, problems such as generation of hydrofluoric acid gas can be solved.
  • the silane-based compound may be trialkylvinylsilane, dialkyldivinylsilane or alkyltrivinylsilane having 1 to 4 carbon atoms in alkyl, or tertiary vinylsilane.
  • the silane-based compound can be used in combination with the compound represented by the formula (1) to form a Si-based SEI coating on the negative electrode, thereby improving the durability of the negative electrode of the battery.
  • the sulfur-containing compound may be represented by the following general formula (4).
  • Y 5 and Y 6 are each independently a direct bond, C or O, and R 5 and R 6 each independently represent a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted 6 to 20 carbon atom An aryl group or a group which is connected to each other to form a ring of a 4-membered to 7-membered ring, and p is 1 or 2.
  • the sulfur-containing compounds of the sulfate series may be methylene sulfate, ethylene sulfate, trimethylene sulfate, tetramethylene sulfate, or sulfates in which substituents are bonded to the alkylene groups.
  • Sulfite-based sulfur- Methylene sulfite, ethylene sulfite, trimethylene sulfite, tetramethylene sulfite or a sulfite having a substituent bonded to these alkylene groups may be applied.
  • the sulfone-based sulfur-containing compound may be a dialkylsulfone in which an alkyl group having 1 to 5 carbon atoms is bonded, a diarylsulfone in which an aryl group having 6 to 12 carbon atoms is bonded, or a sulfone in which a substituent is bonded to the dialkyl or diaryl
  • the sulfur-containing compound of the sultone series may be 1,3-propane sultone, 1,3-propanesultone, 1,4-butane sultone, 1,5-pentane sultone, Sulthone can be applied.
  • the sulfur-containing compounds can generally serve to complement the formation of the SEI film on the surface of the anode, and contribute to the formation of a stable SEI film in the same manner as the compound represented by the above-mentioned formula (1) Effect can be expressed.
  • the nitrile compound is a compound represented by the following formula (5).
  • R 7 is an alkylene group having 1 to 5 carbon atoms.
  • the nitrile compound is a compound containing two nitrile groups, and the linking group connecting two nitrile groups is an alkylene group and the number of carbon atoms is 1 to 5, preferably 2 to 4.
  • the nitrile compound having 2 to 4 carbon atoms in the alkylene group as the linking group is succinonitrile, glutarnitrile or adiponitrile, and may include at least one of these compounds as an element of the electrolyte additive composition. Of these, succinonitrile or adiponitrile may preferably be applied.
  • the nitrile compound can be used in combination with the compound of the formula (1) as described above to provide a synergistic effect on the performance improvement of the lithium secondary battery, and can achieve the same effect as inhibition of the dissolution of the positive electrode transition metal.
  • the nitrile compound when used together with the compound of the above-mentioned formula (1), effects such as improvement in high temperature characteristics can be expected by stabilizing the positive / negative film. That is, the nitrile compound can act as a complement to the negative electrode SEI coating in addition to the effect of expressing the compound of Formula 1, and can act to suppress the decomposition of the solvent in the electrolyte, It is possible to improve the mobility of the user.
  • the fluorinated benzene compound may be a benzene compound in which fluorine is substituted for hydrogen, such as fluorobenzene, difluorobenzene, and trifluorobenzene.
  • the electrolyte additive composition contains the compound represented by Formula 1 and the non-lithium type additive
  • a stable and rigid SEI coating can be formed on the surfaces of the positive and negative electrodes,
  • the side reaction such as decomposition at the periphery can be suppressed and thus even if stored for a long time in a high temperature environment, the gas generation amount can be remarkably reduced.
  • Such an improvement in the storage characteristics leads to an effect of increasing the reversible capacity and improving the lifetime characteristics Can be obtained.
  • the lithium type additive is a compound capable of synergizing with the improvement of the performance of the lithium secondary battery of the compound of Formula 1. Specifically, it has an effect of expressing the compound of Formula 1 and forms SEI film on the surface of the negative electrode, It can serve as a complementary agent for suppressing the decomposition of the solvent in the electrolyte solution and improving the mobility of lithium ions.
  • the content of the lithium-based additive relative to the compound represented by the general formula (1) is not particularly limited, but when it is included in the non-aqueous electrolyte, a content of about 0.01 to 10% by weight, based on the total weight of the non- , Preferably 0.05% to 10% by weight, more preferably 0.1% to 8% by weight, and more preferably 0.1% to 5% by weight. If the content of the lithium-based additive is less than 0.01% by weight, the effect of charging the lithium-based additive is insignificant. If the content exceeds 10% by weight, side reactions may be caused by excessive additives and the interface resistance of the SEI film may increase. The overall performance such as characteristics may be degraded.
  • lithium-based additive examples include boron halide-based lithium, boron oxalate-based lithium, imidazole-based lithium, phosphate-based lithium, and sulfate-based lithium, and mixtures of at least one selected from these may be applied.
  • the present invention is not limited to these compounds, and it is possible to complement the performance improving effect of the compound represented by Chemical Formula 1 and to use boron halide- , Phosphate-based compounds, and the like.
  • lithium tetrafluoroborate lithium tetrachloroborate
  • lithium chlorotrifluoroborate lithium trichlorofluoroborate
  • lithium dichlorodifluoroborate lithium dichlorodifluoroborate
  • the boron oxalate-based lithium may be lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, or lithium dichloro (oxalato) borate.
  • the phosphate-based lithium may be, for example, lithium dihalophosphate, lithium dialkyl phosphate, lithium dihalo (bisoxalato) phosphate and lithium dialkyl (bisoxalato) phosphate,
  • dihalo in the name may be substituted with two halogen substituents, each independently F or Cl, and " dialkyl " means two alkyl substituents each independently an alkyl group having 1 to 3 carbon atoms.
  • the above-mentioned sulfate-based lithium may include a lithium alkylsulfate.
  • alkyl may be an alkyl group having 1 to 3 carbon atoms as an alkyl substituent.
  • the nonaqueous electrolyte solution for a lithium secondary battery of the present invention may include a first additive, which is a compound represented by the formula (1), and at least one second additive selected from non-lithium type additive and / or lithium type additive,
  • the first and second additives may be contained in an amount of preferably 0.01 wt% to 10 wt%, based on the total weight of the non-aqueous electrolyte, as described above.
  • the total content of the first additive and the second additive is less than 20% by weight, specifically about 0.1% to 20% by weight, more specifically 0.1% to 16% by weight based on the total weight of the nonaqueous electrolyte solution It needs to be adjusted.
  • the weight ratio of the non-lithium type additive to the lithium type additive may be from 0: 100 to 100: 0.
  • the weight ratio of the non-lithium type additive to the lithium type additive may be in the range of 0:
  • the mixing ratio can be appropriately adjusted.
  • the lithium salt may be any of those conventionally used for an electrolyte for a lithium secondary battery, and includes, for example, Li + as a cation and 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 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO
  • the lithium salt may be LiCl, LiBr, LiI, LiBF 4 , LiClO 4 , LiAlO 4 , LiAlCl 4 , LiPF 6 , LiSbF 6 , LiAsF 6 , LiB 10 Cl 10 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2, LiN (SO 2 CF 3) 2 (lithium (bis) trifluoromethanesulfonimide, LiTFSI), LiN (SO 2 F) 2 (lithium fluorosulfonyl imide, LiFSI), LiCH 3 SO 3 and LiN (SO 2 CF 2 CF 3 ) 2 (lithium bisperfluoroethanesulfonimide, LiBETI), or a mixture of two or more thereof.
  • the electrolyte salt may include a single substance or a mixture of two or more selected from the group consisting of LiPF 6 , LiBF 4 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiCH 3 SO 3 , LiFSI, LiTFSI and LiBETI.
  • the lithium salt may be appropriately changed within a usable range. However, in order to obtain an effect of forming an anti-corrosive film on the optimum electrode surface, the lithium salt may be contained in the electrolyte at a concentration of 0.8 M to 1.5 M. If the concentration of the electrolyte salt exceeds 1.5M, the concentration of the nonaqueous electrolyte solution may increase to lower the wettability or decrease the film forming effect.
  • the organic solvent is not limited as long as it can minimize decomposition due to an oxidation reaction during charging and discharging of the secondary battery, and can exhibit desired properties together with additives.
  • ether type solvents, ester type organic solvents, and amide type organic solvents may be used singly or in combination of two or more kinds.
  • any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether, methyl propyl ether and ethyl propyl ether, or a mixture of two or more thereof may be used , But is not limited thereto.
  • ester organic solvent may include at least one compound selected from the group consisting of a cyclic carbonate organic solvent, a linear carbonate organic solvent, a linear ester organic solvent, and a cyclic ester organic solvent.
  • cyclic carbonate-based organic solvent examples include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2- Terephthalene carbonate, tilene carbonate, 2,3-pentylene carbonate, vinylene carbonate, and fluoroethylene carbonate (FEC), or a mixture of two or more thereof.
  • EC ethylene carbonate
  • PC propylene carbonate
  • 1,2-butylene carbonate 2,3-butylene carbonate
  • 1,2- Terephthalene carbonate tilene carbonate
  • 2,3-pentylene carbonate vinylene carbonate
  • FEC fluoroethylene carbonate
  • linear carbonate-based organic solvent examples include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl carbonate and ethyl propyl carbonate , Or a mixture of two or more of them may be used.
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • methyl propyl carbonate and ethyl propyl carbonate methyl propyl carbonate and ethyl propyl carbonate
  • the present invention is not limited thereto.
  • linear ester organic solvent examples include any one selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, and butyl propionate, A mixture of two or more of them may be used as typical examples, but the present invention is not limited thereto.
  • cyclic ester organic solvent examples include any one selected from the group consisting of? -Butyrolactone,? -Valerolactone,? -Caprolactone,? -Valerolactone and? -Caprolactone, or 2 Mixtures of two or more species may be used, but are not limited thereto.
  • the cyclic carbonate compound is a highly viscous organic solvent having a high dielectric constant and can dissociate the lithium salt in the electrolyte well. Therefore, the cyclic carbonate compound can be preferably used in a low viscosity such as dimethyl carbonate and diethyl carbonate, When a low-dielectric-constant linear carbonate compound and a linear ester compound are mixed in an appropriate ratio, an electrolyte having a high electric conductivity can be prepared, which is more preferably used.
  • the organic solvent may be a mixed organic solvent obtained by mixing three kinds of carbonate-based solvents, and may be more preferable when using a ternary non-aqueous organic solvent.
  • a lithium secondary battery comprising the above-described electrolyte for a lithium secondary battery, wherein the lithium secondary battery comprises a cathode including a cathode active material, a cathode including a cathode active material, A separator and the above-described electrolyte.
  • the lithium secondary battery of the present invention can be produced by a conventional method known in the art.
  • a porous separator may be placed between an anode and a cathode, and an electrolyte in which a lithium salt is dissolved may be added.
  • the positive electrode may be produced by forming a positive electrode mixture layer on the positive electrode collector.
  • the positive electrode mixture layer may be formed by coating a positive electrode slurry containing a positive electrode active material, a binder, a conductive material and a solvent on a positive electrode collector, followed by drying and rolling.
  • the positive electrode collector is not particularly limited as long as it has electrical conductivity without causing chemical change in the battery.
  • the positive electrode collector may be formed of a metal such as carbon, stainless steel, aluminum, nickel, titanium, sintered carbon, , Nickel, titanium, silver, or the like may be used.
  • the cathode active material is a compound capable of reversibly intercalating and deintercalating lithium, and may specifically include a lithium composite metal oxide including lithium and at least one metal such as cobalt, manganese, nickel, or aluminum have. More specifically, the lithium composite metal oxide may be at least one selected from the group consisting of lithium-manganese-based oxides (for example, LiMnO 2 and LiMn 2 O 4 ), lithium-cobalt oxides (for example, LiCoO 2 ), lithium- (for example, LiNiO 2 and the like), lithium-nickel-manganese-based oxide (for example, LiNi 1-Y Mn Y O 2 (where, 0 ⁇ Y ⁇ 1), LiMn 2-z Ni z O 4 ( here, 0 ⁇ Z ⁇ 2) and the like), lithium-nickel-cobalt oxide (e.
  • LiMnO 2 and LiMn 2 O 4 lithium-cobalt oxides
  • LiCoO 2 lithium-
  • lithium-manganese-cobalt oxide e. g., (in which LiCo 1-Y2 Mn Y2 O 2 , 0 ⁇ Y2 ⁇ 1), LiMn 2-z1 Co z1 O 4 ( here, 0 ⁇ z1 ⁇ 2) and the like
  • the lithium composite metal oxide may be LiCoO 2 , LiMnO 2 , LiNiO 2 , lithium nickel manganese cobalt oxide (for example, 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 ), or lithium nickel cobalt aluminum oxide (e.g., Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.) and the like.
  • lithium nickel cobalt aluminum oxide e.g., Li (Ni 0.8 Co 0.15 Al 0.05 ) O 2, etc.
  • the positive electrode active material may include 80 wt% to 99.5 wt%, specifically 85 wt% to 95 wt%, based on the total weight of the solid content in the positive electrode slurry.
  • the content of the cathode active material is 80 wt% or less, the energy density is lowered and the capacity may be lowered.
  • the binder is a component that assists in bonding of the active material to the conductive material and bonding to the current collector, and is usually added in an amount of 1 to 30 wt% based on the total weight of the solid content in the positive electrode slurry. If the binder is less than 1 wt%, the adhesive force between the electrode active material and the current collector may be insufficient. If the binder is more than 30 wt%, the adhesive force may be improved, but the content of the electrode active material may be decreased.
  • binders examples include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene (Ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethylcellulose
  • EPDM tetrafluoroethylene
  • EPDM tetrafluoroethylene
  • EPDM sulfonated EPDM
  • styrene-butadiene rubber fluorine rubber
  • fluorine rubber various copolymers and the like.
  • the conductive material may be added in an amount of 1 to 20 wt% based on the total weight of the solid content in the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has electrical conductivity without causing chemical changes in the battery, and examples thereof include carbon black, acetylene black (or denka black), Ketjenblack, channel black, furnace black, Carbon black such as lamp black or thermal black; Graphite powder such as natural graphite, artificial graphite, or graphite with a highly developed crystal structure; Conductive fibers such as carbon fiber and metal fiber; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the conductive material is usually added in an amount of 0.5% by weight to 50% by weight, specifically 1% by weight to 15% by weight, more specifically 3% by weight to 10% by weight, based on the total weight of the solid content in the positive electrode slurry. If the content of the conductive material is less than 0.5% by weight, the effect of improving the electrical conductivity may not be expected or the electrochemical characteristics of the battery may be deteriorated. If the content of the conductive material is more than 50% by weight, And the capacity and the energy density may be lowered.
  • the conductive material may be selected from acetylene black (manufactured by Chevron Chemical Company, manufactured by Denka Singapore Private Limited or Gulf Oil Company), Ketchen Black EC (manufactured by Armak Company), Vulcan XC-72 (manufactured by Cabot Company) (Super) -P (manufactured by Timcal) or the like may be used.
  • a filler may be further added to the mixture.
  • the filler is optionally used as a component for suppressing the expansion of the anode, and is not particularly limited as long as it is a fibrous material without causing a chemical change in the battery.
  • the filler include olefin polymers such as polyethylene and polypropylene; Fibrous materials such as glass fibers and carbon fibers are used.
  • Examples of the solvent for forming the positive electrode include organic solvents such as NMP (N-methylpyrrolidone), DMF (dimethylformamide), acetone, and dimethylacetamide, and water. These solvents may be used alone or in combination of two or more Can be mixed and used.
  • organic solvents such as NMP (N-methylpyrrolidone), DMF (dimethylformamide), acetone, and dimethylacetamide, and water. These solvents may be used alone or in combination of two or more Can be mixed and used.
  • the amount of the solvent to be used may be an amount having a viscosity sufficient to dissolve and disperse the electrode active material, the binder, and the conductive agent in consideration of the coating thickness of the slurry and the production yield.
  • the solid content in the slurry containing the cathode active material, and optionally the binder and the conductive material may be 10 wt% to 60 wt%, preferably 20 wt% to 50 wt%.
  • the cathode can be produced by a conventional method known in the art. For example, by forming a negative electrode mixture layer on the negative electrode collector.
  • the negative electrode material mixture layer may be formed by coating an anode current collector with a negative electrode slurry including a negative electrode active material, a binder, a conductive material, and a solvent, followed by drying and rolling.
  • the anode current collector generally has a thickness of 3 to 500 mu m.
  • the negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • Examples of the negative electrode current collector include copper, stainless steel, aluminum, nickel, titanium, sintered carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver or the like, aluminum-cadmium alloy, or the like can be used.
  • fine unevenness can be formed on the surface to enhance the bonding force of the negative electrode active material, and it can be used in various forms such as films, sheets, foils, nets, porous bodies, foams and nonwoven fabrics.
  • the negative electrode active material may be a lithium metal, a carbon material capable of reversibly intercalating / deintercalating lithium ions, a metal or an alloy of these metals and lithium, a metal complex oxide, lithium capable of doping and dedoping lithium Materials, and transition metal oxides.
  • the carbonaceous material capable of reversibly intercalating / deintercalating lithium ions is not particularly limited as long as it is a carbonaceous anode active material generally used in a lithium ion secondary battery.
  • the carbonaceous material include crystalline carbon, Amorphous carbon or any combination thereof.
  • the crystalline carbon include graphite such as natural graphite or artificial graphite in the form of amorphous, plate-like, flake, spherical or fiber, and examples of the amorphous carbon include soft carbon (soft carbon) Or hard carbon, mesophase pitch carbide, fired coke, and the like.
  • the metal or an alloy of these metals and lithium may be selected from the group consisting of Cu, Ni, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, And Sn, or an alloy of these metals and lithium may be used.
  • metal composite oxide is 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? X? 1), and Sn x Me 1-x Me y y z , Pb, Ge, Me ': Al, B, P, Si, Group 1, Group 2, Group 3 elements of the periodic table, Halogen: 0 ⁇ x? 1; 1? Y? May be used.
  • Si As the material capable of doping and dedoping lithium, Si, SiO x (0 ⁇ x? 2), Si-Y alloy (Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si), Sn, SnO 2 , Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element and an element selected from the group consisting of combinations thereof, and not Sn), and at least one of them may be mixed with SiO 2 .
  • Si-Y alloy Y is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, Rare earth elements and combinations thereof, but not Si
  • Sn, SnO 2 Sn-Y (wherein Y is at least one element selected from the group consisting of alkali metals, alkaline earth metals, Group 13 elements, Group 14 elements, Element
  • the element Y may be at least one element 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, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Ti, Ge, P, As, Sb, Se, Te, Po, and combinations thereof.
  • transition metal oxide examples include lithium-containing titanium composite oxide (LTO), vanadium oxide, lithium vanadium oxide, and the like.
  • the negative active material may be contained in an amount of 80% by weight to 99% by weight based on the total weight of the solid content in the negative electrode slurry.
  • the binder and the conductive material contained in the cathode may be applied in the same manner as applied to the anode.
  • the solvent may include water or an organic solvent such as NMP, alcohol, etc., and may be used in an amount to make the desired viscosity when the anode active material and, optionally, a binder and a conductive material are included.
  • the slurry containing the negative electrode active material and, optionally, the binder and the conductive material may be contained in such a manner that the solid concentration of the slurry is 50% by weight to 75% by weight, preferably 50% by weight to 65% by weight.
  • a polyolefin separator commonly used in the art or a composite separator having an organic-inorganic hybrid layer formed on an olefin based material may be used without particular limitation .
  • the separator blocks the internal short circuit of both electrodes and impregnates the electrolyte.
  • the separator may be manufactured by preparing a separator composition by mixing a polymer resin, a filler, and a solvent, then coating the separator composition directly on the electrode, Drying the solution to form a separator film, or casting and drying the separator composition on a support, and then laminating the separator film separated from the support on the electrode.
  • the separator may be a porous polymer film commonly used, such as a porous polymer film made of a polyolefin-based polymer such as an ethylene homopolymer, a propylene homopolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / methacrylate copolymer
  • the polymer film may be used alone or as a laminate thereof, or may be a nonwoven fabric made of a conventional porous nonwoven fabric, for example, glass fiber of high melting point, polyethylene terephthalate fiber or the like, but is not limited thereto.
  • the pore diameter of the porous separation membrane is generally 0.01 to 50 ⁇ m, and the porosity may be 5 to 95%.
  • the thickness of the porous separator may be generally in the range of 5 to 300 mu m.
  • the pouch type battery may be manufactured by storing the positive electrode, the negative electrode, and the separator having the above structure in the pouch case and then injecting the non-aqueous electrolyte.
  • the present invention is not limited thereto, There is no particular limitation, and a cylindrical shape or a square shape using a can can be applied, and a coin shape or the like can be applied.
  • EC ethyl carbonate
  • EMC ethyl methyl carbonate
  • the slurry of the cathode active material was prepared by mixing 40 g of the slurry of the cathode active material.
  • the positive electrode active material slurry was applied to a positive electrode current collector (Al thin film) having a thickness of 100 m, dried, and roll pressed to produce a positive electrode.
  • a negative electrode active material slurry obtained by mixing natural graphite as a negative active material, PVDF as a binder and carbon black as a conductive material in a ratio of 95: 2: 3 (wt%) was mixed with 100 g of N-methyl-2-pyrrolidone (NMP) To prepare a negative electrode active material slurry.
  • NMP N-methyl-2-pyrrolidone
  • the negative electrode active material slurry was coated on a negative electrode current collector (Cu thin film) having a thickness of 90 ⁇ , dried, and rolled to produce a negative electrode.
  • a positive electrode and a negative electrode prepared by the above-mentioned method were co-produced with a polyethylene porous film by a conventional method, and then the prepared non-aqueous electrolyte was injected to prepare a lithium secondary battery.
  • a nonaqueous electrolytic solution and its equivalent were prepared in the same manner as in Example 1, except that 0.1 g of the compound of formula (Ia) as the first additive and 1 g of the second additive (FEC) were added to 98.9 g of the organic solvent in the preparation of the non- A lithium secondary battery was prepared (see Table 1).
  • a nonaqueous electrolytic solution and a lithium secondary battery having the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that 2 g of the compound (1a) as the first additive was added to 98 g of the organic solvent in the preparation of the nonaqueous electrolyte (see Table 1 Reference).
  • a nonaqueous electrolytic solution and a lithium secondary battery having the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that 5 g of the compound of Formula 1a as the first additive was added to 95 g of the organic solvent in the preparation of the nonaqueous electrolyte solution Reference).
  • a nonaqueous electrolytic solution and a lithium secondary battery comprising the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that 6 g of the compound (1a) as the first additive was contained in 94 g of the organic solvent in the preparation of the nonaqueous electrolyte (see Table 1 Reference).
  • a nonaqueous electrolytic solution and a lithium secondary battery having the nonaqueous electrolyte solution were prepared in the same manner as in Example 1 except that 7 g of the compound of Formula 1a as the first additive was added to 93 g of the organic solvent in the preparation of the nonaqueous electrolyte solution Reference).
  • a nonaqueous electrolytic solution and a lithium secondary battery having the nonaqueous electrolytic solution were prepared in the same manner as in Example 1 except that additives were not included in the preparation of the nonaqueous electrolyte (see Table 1).
  • a nonaqueous electrolytic solution and a lithium secondary battery having the nonaqueous electrolytic solution were prepared in the same manner as in Comparative Example 1, except that 1 g of fluoroethylene carbonate as a second additive was added to 99 g of an organic solvent in the preparation of the nonaqueous electrolyte (see Table 1 Reference).
  • the lithium secondary batteries manufactured in Examples 1 to 6 and the lithium secondary batteries prepared in Comparative Examples 1 and 2 were charged at 4.degree. C./4.14 V constant current / constant voltage (CC / CV) conditions at 45.degree. And discharging to 1.0 V at 3.0 V was repeated 200 times, and the capacity retention rate was calculated using the following formula 1. The results are shown in Table 1 below.
  • Capacity retention rate (%) [(discharge capacity after 200 cycles (mAh)) / (discharge capacity after 1 cycle (mAh))] 100
  • the lithium secondary batteries prepared in Examples 1 to 6 and the lithium secondary batteries prepared in Comparative Examples 1 and 2 were charged at a constant current of 0.2 C / 4.45 V under a constant current / constant voltage (CC / CV) condition up to 4.45 V /
  • the initial discharge capacity was measured by discharging to 3.0 V at 0.2C.
  • the battery was charged to 4.45 V / 112 mA under a constant current / constant voltage (CC / CV) condition of 0.2 C / 4.45 V at room temperature, and then stored at 60 ° C. for 4 weeks. Then, the secondary batteries were charged to 4.45 V / 112 mA at a constant current / constant voltage (CC / CV) condition of 0.2 C / 4.45 V at room temperature, discharged to 0.2 C at 3.0 V, 2 was used to calculate the capacity retention rate.
  • CC / CV constant current / constant voltage
  • Capacity retention rate (%) [discharge capacity (mAh) / initial discharge capacity after 4 weeks storage (mAh)] ⁇ 100
  • each battery was set to SOC 50% based on a discharging capacity, and the thickness was measured and defined as an initial thickness. Subsequently, the battery was stored at 60 DEG C for 4 weeks at high temperature, and the measured cell thickness was defined as the final thickness.
  • the thickness increase rate (%) of the battery was calculated using the following formula 3, and the results are shown in Table 1 below.
  • Thickness increase rate (%) [(final thickness - initial thickness) / initial thickness] x 100
  • Resistance increase rate (%) [(discharge resistance after 4 weeks - first discharge resistance) / (first discharge resistance)] ⁇ 100
  • the capacity retention rate of the secondary battery comprising the nonaqueous electrolyte prepared in Examples 1 to 5 was about 81.6% or more, The non-aqueous electrolytic solution of Comparative Example 1 and Comparative Example 2 having the non-aqueous electrolyte solution of Comparative Example 1 and Comparative Example 2 was improved.
  • the secondary batteries having the nonaqueous electrolyte prepared in Examples 1 to 5 had a capacity retention ratio of about 82.3% or more after storage at 60 DEG C, while the nonaqueous electrolyte prepared in Comparative Examples 1 and 2 It can be seen that the secondary battery with the electrolyte deteriorated to about 72.5% or less.
  • the resistance increase rate and the battery thickness increase rate after storage for 4 weeks at a high temperature of 60 ⁇ in the non-aqueous electrolyte prepared in Examples 1 to 5 were about 26.3% And the thickness increase rate was about 20.6% or less.
  • the secondary battery with the non-aqueous electrolyte prepared in Comparative Examples 1 and 2 showed that the resistance increase rate was about 34.2% or more and the thickness increase rate was about 28.1% .
  • the resistance increase rate was 26.1% by the first additive added in an excess amount, and was equal to that of the lithium secondary batteries prepared in Examples 1 to 5, Was about 12.4%, which was slightly improved compared with the lithium secondary batteries prepared in Examples 1 to 5.

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Abstract

La présente invention porte sur un additif de solution d'électrolyte non-aqueux, une solution d'électrolyte non-aqueux pour un accumulateur au lithium le contenant, et un accumulateur au lithium, et plus précisément, en réalisant la solution d'électrolyte non-aqueux contenant un composé pouvant accroître l'effet de formation d'une pellicule de SEI sur la surface d'une électrode positive et d'une électrode négative pour pouvoir maintenir un effet passif, la caractéristique d'accumulation à haute température et les caractéristiques de longévités de l'accumulateur au lithium peuvent être améliorées.
PCT/KR2018/007530 2017-07-03 2018-07-03 Additif d'électrolyte et solution d'électrolyte non-aqueux pour accumulateur au lithium le contenant WO2019009595A1 (fr)

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CN201880003987.9A CN109891654B (zh) 2017-07-03 2018-07-03 电解质添加剂和包括该添加剂的用于锂二次电池的非水电解质溶液
JP2019528062A JP7034404B2 (ja) 2017-07-03 2018-07-03 電解質添加剤およびそれを含むリチウム二次電池用非水電解液
PL18828080.4T PL3512028T3 (pl) 2017-07-03 2018-07-03 Dodatek do elektrolitu i niewodny roztwór elektrolitu dla akumulatora litowego i zawierający go akumulator litowy
ES18828080T ES2929134T3 (es) 2017-07-03 2018-07-03 Aditivo de electrolito y disolución de electrolito no acuoso para batería secundaria de litio que lo contiene
EP18828080.4A EP3512028B1 (fr) 2017-07-03 2018-07-03 Additif d'électrolyte et solution d'électrolyte non-aqueux pour accumulateur au lithium le contenant
US16/339,537 US11063296B2 (en) 2017-07-03 2018-07-03 Electrolyte additive and non-aqueous electrolyte solution for lithium secondary battery comprising the same

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