WO2022265259A1 - 리튬이차전지용 전해질 및 이를 포함하는 리튬이차전지 - Google Patents
리튬이차전지용 전해질 및 이를 포함하는 리튬이차전지 Download PDFInfo
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- WO2022265259A1 WO2022265259A1 PCT/KR2022/007616 KR2022007616W WO2022265259A1 WO 2022265259 A1 WO2022265259 A1 WO 2022265259A1 KR 2022007616 W KR2022007616 W KR 2022007616W WO 2022265259 A1 WO2022265259 A1 WO 2022265259A1
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- WIPO (PCT)
- Prior art keywords
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- substituted
- unsubstituted
- electrolyte
- lithium secondary
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 100
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 99
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- 150000001875 compounds Chemical class 0.000 claims abstract description 121
- 239000000654 additive Substances 0.000 claims abstract description 93
- 230000000996 additive effect Effects 0.000 claims abstract description 81
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910000077 silane Inorganic materials 0.000 claims abstract description 39
- 150000003457 sulfones Chemical class 0.000 claims abstract description 39
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 21
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 6
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 6
- 229940126214 compound 3 Drugs 0.000 claims description 39
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 229940125904 compound 1 Drugs 0.000 claims description 37
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 239000007773 negative electrode material Substances 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000001072 heteroaryl group Chemical group 0.000 claims description 13
- 125000004122 cyclic group Chemical group 0.000 claims description 12
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- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 3
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- 230000000052 comparative effect Effects 0.000 description 44
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Images
Classifications
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- 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
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- 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
- It relates to an electrolyte for a lithium secondary battery and a lithium secondary battery including the same.
- Lithium secondary batteries have more than three times higher energy density per unit weight compared to conventional lead-acid batteries, nickel-cadmium batteries, nickel-metal hydride batteries, and nickel-zinc batteries, and are capable of high-speed charging.
- a lithium secondary battery must be stable within an operating voltage range of the battery and must maintain safety even beyond the operating voltage range.
- excessive lithium is extracted from the positive electrode and excessively inserted into the negative electrode under an overcharge and overvoltage environment. Due to this, both the anode and the cathode are in an unstable state.
- One aspect is to provide an electrolyte for a lithium secondary battery including a novel electrolyte additive.
- Another aspect is to provide a lithium secondary battery including the electrolyte.
- a sulfone-based compound additive having at least one phenyl group and a silane-based compound additive having at least one phenyl group; containing, an electrolyte for a lithium secondary battery is provided.
- the sulfone-based compound additive may be a compound represented by Formula 1 below:
- R 1 , R 2 are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, or a substituted or unsubstituted C3-C20 cyclo An alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group,
- At least one of R 1 and R 2 may be a C6 aryl group unsubstituted or substituted with a halogen element.
- the sulfone-based compound additive may include a compound represented by Formula 1-1 below:
- R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , At least one of R' 9 and R' 10 may be a fluorine atom.
- the silane-based compound additive may be a compound represented by Formula 2 below:
- At least one of R 3 , R 4 , R 5 , and R 6 may be a substituted or unsubstituted C6 aryl group.
- the silane-based compound additive may include a compound represented by Formula 2-1 below:
- the sulfone-based compound additive may include at least one of the following compounds 1 and 2, and the silane-based compound additive may include at least one of the following compounds 3 and 4:
- the weight ratio of the sulfone-based compound additive to the silane-based compound additive may be 1:7 to 7:1.
- the total amount of the sulfone-based compound additive and the silane-based compound additive may be 0.1 to 10 parts by weight based on 100 parts by weight of the total electrolyte.
- a positive electrode including a positive electrode active material
- a negative electrode including a negative electrode active material
- a lithium secondary battery including the above-described electrolyte disposed between the positive electrode and the negative electrode.
- An electrolyte for a lithium secondary battery includes a sulfone-based compound additive having at least one phenyl group and a silane-based compound additive having at least one phenyl group.
- the lithium secondary battery including the electrolyte forms a film on the positive electrode under an overcharge and overvoltage environment to protect the positive electrode and suppresses electrolyte decomposition by suppressing a voltage rise of the battery. Therefore, the lithium secondary battery maintains low-temperature (-10 ° C) discharge capacity (ratio), high-temperature (60 ° C) storage characteristics, and high-temperature (45 ° C) life characteristics or improves overcharge characteristics while minimizing the degradation of the above performances Thus, safety can be improved.
- FIG. 1 is a schematic diagram of a lithium secondary battery according to an embodiment.
- the overcharge property improving additive has a structure containing a biphenyl group. If the overcharge characteristic improving additive is included in the electrolyte, the lithium secondary battery including the additive has a problem in that electrolyte decomposition starts even within a normal operating voltage range, increasing cell internal resistance and deteriorating performance such as life characteristics.
- An electrolyte for a lithium secondary battery includes a lithium salt; non-aqueous organic solvent; and a sulfone-based compound additive having at least one phenyl group and a silane-based compound additive having at least one phenyl group.
- An electrolyte for a lithium secondary battery includes a sulfone-based compound additive having at least one phenyl group and a silane-based compound additive having at least one phenyl group.
- the sulfone-based compound additive having one or more phenyl groups forms a film on the positive electrode and serves to protect the positive electrode in an overcharged and overvoltage environment.
- the silane-based compound additive having one or more phenyl groups serves to prevent electrolyte decomposition by suppressing an increase in voltage of a battery under an overcharge and overvoltage environment.
- the lithium secondary battery including the electrolyte can improve safety by improving overcharge characteristics, and at the same time, low temperature (-10 °C) discharge capacity (ratio), high temperature (60 °C) storage characteristics, and high temperature (45 °C) lifespan It is possible to maintain the performance of the characteristic or to minimize degradation of the performance.
- the sulfone-based compound additive may be a compound represented by Formula 1 below:
- R 1 , R 2 are each independently a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C10 alkynyl group, or a substituted or unsubstituted C3-C20 cyclo An alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C6-C50 alkylaryl group, or a substituted or unsubstituted C6-C50 heteroaryl group,
- At least one of R 1 and R 2 may be a C6 aryl group unsubstituted or substituted with a halogen element.
- the sulfone-based compound additive may include a compound represented by Chemical Formula 1-1:
- R' 1 , R' 2 , R' 3 , R' 4 , R' 5 , R' 6 , R' 7 , R' 8 , At least one of R' 9 and R' 10 may be a fluorine atom.
- the sulfone-based compound additive forms a film on the surface of the positive electrode and acts as a protective film that blocks active sites on the surface of the positive electrode to prevent some of the transition metal from being eluted and deposited on the negative electrode during charging and discharging, and generated between the electrolyte and the positive electrode. It is possible to improve high-temperature performance and overcharge characteristics by suppressing side reactions and gas generation.
- the silane-based compound additive may include a compound represented by Formula 2-1 below:
- the silane-based compound additive is partially reduced and decomposed on the negative electrode during initial charging, so that a suitable ion-conductive protective film is formed on the negative electrode surface and prevents electrolyte decomposition by suppressing a voltage rise even under an overcharging environment.
- the sulfone-based compound additive may include one or more of the following compounds 1 and 2
- the silane-based compound additive may include one or more of the following compounds 3 and 4:
- the weight ratio of the sulfone-based compound additive to the silane-based compound additive may be 1:7 to 7:1.
- the weight ratio of the sulfone-based compound additive and the silane-based compound additive may be 1:5 to 5:1 or 1:3 to 3:1.
- the lithium secondary battery including the same maintains low temperature (-10 ° C) discharge capacity (ratio), high temperature (60 ° C) storage characteristics, and high temperature (45 ° C) life characteristics, or lowers the above performances Safety can be maximized by improving overcharge characteristics while minimizing .
- a total amount of the sulfone-based compound additive and the silane-based compound additive may be 0.1 to 10 parts by weight based on 100 parts by weight of the total electrolyte.
- the total content of the sulfone-based compound additive and the silane-based compound additive may be 0.1 to 9 parts by weight, 0.1 to 8 parts by weight, 0.1 to 7 parts by weight, or 0.1 to 9 parts by weight based on 100 parts by weight of the total electrolyte. It can be 6 parts by weight or it can be 0.1 to 5 parts by weight or it can be 0.1 to 4 parts by weight or it can be 0.1 to 3 parts by weight or it can be 0.1 to 2 parts by weight or it can be 0.1 to 1 parts by weight.
- the lithium secondary battery including the same maintains the performance of low temperature (-10 °C) discharge capacity (ratio), high temperature (60 °C) storage characteristics, and high temperature (45 °C) life characteristics, or deterioration of the above performances Safety can be maximized by improving overcharge characteristics while minimizing .
- the lithium salt is a lithium cation
- the non-aqueous organic solvent may be a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, aprotic solvent, or a combination thereof.
- the non-aqueous organic solvent included in the lithium secondary battery electrolyte serves as a medium through which ions involved in the electrochemical reaction of the battery can move, and the non-aqueous organic solvent used in the present invention is commonly used in the art If it is, it is not particularly limited.
- the carbonate-based solvent includes dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC) , Ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), etc.
- DMC dimethyl carbonate
- DEC diethyl carbonate
- DPC dipropyl carbonate
- MPC methylpropyl carbonate
- EPC ethylpropyl carbonate
- MEC methylethyl carbonate
- Ethylene carbonate EC
- PC propylene carbonate
- BC butylene carbonate
- the ester-based solvent includes methyl acetate, ethyl acetate, n-propyl acetate, dimethyl acetate, methyl propionate, Ethyl propionate, propyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone, caprolactone and the like can be used.
- Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, etc. may be used as the ether-based solvent, and cyclohexanone or the like may be used as the ketone-based solvent. there is.
- ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol-based solvent, and as the aprotic solvent, R-CN (R is a straight-chain, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms, , double bonded aromatic rings or ether bonds), nitriles such as dimethylformamide, amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, etc. may be used. .
- R-CN R is a straight-chain, branched, or cyclic hydrocarbon group having 2 to 20 carbon atoms, , double bonded aromatic rings or ether bonds
- nitriles such as dimethylformamide, amides such as dimethylformamide, dioxolanes such as 1,3-dioxolane, sulfolanes, etc.
- the non-aqueous organic solvents may be used alone or in combination of two or more, and the mixing ratio when two or more are used in combination can be appropriately adjusted according to the desired battery performance, which is difficult for those skilled in the art to use. can be widely understood.
- the carbonate-based solvent it is preferable to use a mixture of cyclic carbonate and chain carbonate.
- the cyclic carbonate and the chain carbonate are mixed in a volume ratio of 1:1 to 1:9, the performance of the electrolyte may be excellent.
- the non-aqueous organic solvent of the present invention may further include an aromatic hydrocarbon-based organic solvent in addition to the carbonate-based solvent.
- the carbonate-based solvent and the aromatic hydrocarbon-based organic solvent may be mixed in a volume ratio of 1:1 to 30:1.
- the aromatic hydrocarbon-based organic solvent is benzene, fluorobenzene, 1,2-difluorobenzene, 1,3-difluorobenzene, 1,4-difluorobenzene, 1,2,3-trifluorobenzene , 1,2,4-trifluorobenzene, chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2,3-trichlorobenzene, 1,2, 4-trichlorobenzene, iodobenzene, 1,2-diiodobenzene, 1,3-diiodobenzene, 1,4-diiodobenzene, 1,2,3-triiodobenzene, 1,2,4 -triiodobenzene, toluene, fluorotoluene, 1,2-difluorotoluene, 1,3-difluorotol
- the non-aqueous organic solvent is ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonate, dimethyl carbonate (DMC), diethyl carbonate (DEC), Dipropylcarbonate, Vinylethylene Carbonate (VEC), Butylene Carbonate, Ethyl Propionate (EP), Propyl Propionate (PP), Ethyl Butyrate, Dimethylsulfoxide, Dimethylformamide, Dimethylacetamide, Gamma-Valero It may contain at least one selected from lactone, gamma-butyrolactone, and tetrahydrofuran. However, it is not limited thereto, and all non-aqueous organic solvents usable in the art may be used.
- the electrolyte may be in a liquid or gel state.
- a lithium secondary battery includes a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; And it may include the above-mentioned electrolyte disposed between the positive electrode and the negative electrode.
- the shape of the lithium secondary battery is not particularly limited, and includes lithium secondary batteries such as lithium ion batteries, lithium ion polymer batteries, and lithium sulfur batteries.
- the lithium secondary battery including the above-described electrolyte, maintains the performance of low temperature (-10 °C) discharge capacity (ratio), high temperature (60 °C) storage characteristics, and high temperature (45 °C) life characteristics or minimizes the degradation of the above performances Safety can be improved by improving overcharging characteristics while doing so.
- the cathode active material may be selected from compounds represented by the following chemical formulas.
- Li a A 1-b D' b E 2 (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5);
- Li a G 1-b D' b O 2-c E c (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05);
- LiG 2-b D′ b O 4-c E c (wherein 0 ⁇ b ⁇ 0.5 and 0 ⁇ c ⁇ 0.05);
- Li a Ni 1-bc Co b D' c E ⁇ (wherein 0.90 ⁇ a ⁇ 1.8, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05, 0 ⁇ ⁇ ⁇ 2);
- Li a Ni 1-bc Co b D' c O 2- ⁇ J ⁇ (wherein 0.90 ⁇ a ⁇ 1.8
- A is selected from the group consisting of Ni, Co, Mn and combinations thereof
- D' is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, rare earth elements and these Is selected from the group consisting of a combination of
- E is selected from the group consisting of O, F, S, P and combinations thereof
- G is selected from the group consisting of Co, Mn and combinations thereof
- J is It is selected from the group consisting of F, S, P, and combinations thereof
- L is Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr , Mo, W, Sg, Tc, Re, Bh, Fe, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, Si , Ge, Sn, P, As, Sb, Bi, S, Se, Te, Po, M
- the negative active material may include a carbon-based material, a silicon-based material, or a silicon-carbon-based composite.
- the carbon-based material may be crystalline carbon, amorphous carbon, or a mixture thereof.
- the crystalline carbon may be graphite such as amorphous, plate-shaped, flake-shaped, spherical or fibrous natural graphite or artificial graphite, and the amorphous carbon may be soft carbon (low-temperature calcined carbon) or hard carbon (hard carbon). carbon), mesophase pitch carbide, or calcined coke.
- the silicon-based material may include silicon particles, silicon alloy particles, and/or silicon nanowires.
- the silicon-based material may be silicon particles and may have an average particle diameter of 50 nm to 150 nm.
- the silicon-carbon-based composite is a composite having a structure in which silicon nanoparticles are disposed on the carbon-based compound, a composite in which silicon particles are included on the surface of the carbon-based compound and inside, and a silicon particle coated with the carbon-based compound to form the inside of the carbon-based compound It may be a complex included in.
- the carbon-based compound may be graphite, graphene, graphene oxide, or a combination thereof.
- the anode active material may be an active material obtained by dispersing silicon nanoparticles having an average particle diameter of about 200 nm or less on carbon-based compound particles and then coating them with carbon, an active material in which silicon (Si) particles are present on and inside graphite, and the like. there is.
- the silicon nanoparticles may have an average particle diameter of 50 nm to 150 nm.
- An average particle diameter of the silicon-carbon composite may be, for example, 1 ⁇ m to 20 ⁇ m.
- a lithium secondary battery including the anode active material may have improved initial efficiency, capacity, and lifespan characteristics.
- the lithium secondary battery may be manufactured by the following method.
- an anode is prepared.
- the positive electrode is prepared, for example, by the following exemplary method, but is not necessarily limited to this method and is adjusted according to required conditions.
- a cathode active material composition is prepared by mixing the above-described cathode active material, conductive agent, binder, and solvent.
- the prepared cathode active material composition is directly coated on an aluminum current collector and dried to prepare a cathode plate having a cathode active material layer formed thereon.
- the cathode active material composition is cast on a separate support, and then a film obtained by peeling from the support is laminated on the aluminum current collector to prepare a cathode electrode plate having a cathode active material layer formed thereon.
- Examples of the conductive agent include carbon black, graphite particles, natural graphite, artificial graphite, acetylene black, Ketjen black, and carbon fiber; carbon nanotubes; metal powders such as copper, nickel, aluminum, silver, or metal fibers or metal tubes; Conductive polymers such as polyphenylene derivatives are used, but are not limited thereto, and any conductive material used in the art is possible.
- the binder includes vinylidene fluoride/hexafluoropropylene copolymer, polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polytetrafluoroethylene (PTFE), a mixture of the above polymers, and styrene butadiene rubber.
- a polymer or the like is used, and as a solvent, N-methylpyrrolidone (NMP), acetone, water, etc. are used, but are not necessarily limited to these, and all are possible as long as they are used in the art.
- pores in the electrode plate by further adding a plasticizer or a pore former to the cathode active material composition.
- the contents of the positive electrode active material, conductive agent, binder, and solvent used in the positive electrode are at levels commonly used in lithium secondary batteries. Depending on the use and configuration of the lithium secondary battery, one or more of the conductive material, binder, and solvent may be omitted.
- the cathode active material may further include the following cathode active material in addition to the above-described cathode active material.
- the cathode active material is a lithium-containing metal oxide, and any material commonly used in the art may be used without limitation.
- any material commonly used in the art may be used without limitation.
- one or more types of composite oxides of lithium and a metal selected from cobalt, manganese, nickel, and combinations thereof may be used, and specific examples include Li a A 1-b B' b D' 2 (In the above formula, 0.90 ⁇ a ⁇ 1, and 0 ⁇ b ⁇ 0.5); Li a E 1-b B' b O 2-c D' c (wherein 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.5, 0 ⁇ c ⁇ 0.05); LiE 2-b B′ b O 4-c D′ c (wherein 0 ⁇ b ⁇ 0.5 and 0 ⁇ c ⁇ 0.05); Li a Ni 1-bc Co b B' c D' ⁇ (wherein 0.90 ⁇ a ⁇ 1, 0 ⁇ b ⁇
- A is Ni, Co, Mn, or a combination thereof
- B' is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, a rare earth element, or a combination thereof
- D' is O, F, S, P, or a combination thereof
- E is Co, Mn, or a combination thereof
- F' is F, S, P, or a combination thereof
- G is Al, Cr, Mn, Fe, Mg, La, Ce, Sr, V, or combinations thereof
- Q is Ti, Mo, Mn, or a combination thereof
- I' is Cr, V, Fe, Sc, Y, or a combination thereof
- J is V, Cr, Mn, Co, Ni, Cu, or combinations thereof.
- the coating layer added to the surface of the above compound includes, for example, a coating element compound of oxide, hydroxide, oxyhydroxide of the coating element, oxycarbonate of the coating element, or hydroxycarbonate of the coating element. .
- the compound constituting the coating layer is amorphous or crystalline.
- the coating elements included in the coating layer include Mg, Al, Co, K, Na, Ca, Si, Ti, V, Sn, Ge, Ga, B, As, Zr, or mixtures thereof.
- the coating layer formation method is selected within a range that does not adversely affect the physical properties of the cathode active material.
- the coating method is, for example, spray coating, dipping method or the like. Since a specific coating method can be well understood by those skilled in the art, a detailed description thereof will be omitted.
- a negative electrode is prepared as follows.
- the negative electrode is manufactured in substantially the same manner as the positive electrode except for using the negative electrode active material described above instead of the positive electrode active material.
- a negative electrode active material composition is prepared by mixing a negative electrode active material, a conductive agent, a binder, and a solvent, and directly coated on a copper current collector to prepare a negative electrode plate.
- a negative electrode plate is prepared by casting the prepared negative active material composition on a separate support and laminating the negative active material film peeled from the support to a copper current collector.
- Any negative active material can be used as long as it is used as an anode active material for a lithium secondary battery in the art other than the above-described negative active material.
- it includes at least one selected from lithium metal, metals alloyable with lithium, transition metal oxides, non-transition metal oxides, and carbon-based materials.
- the metal alloyable with lithium is, for example, Si, Sn, Al, Ge, Pb, Bi, Sb Si-Y' alloy (Y' is an alkali metal, an alkaline earth metal, a group 13 element, a group 14 element, a transition metal, A rare earth element or a combination thereof, but not Si), a Sn-Y' alloy (wherein Y' is an alkali metal, an alkaline earth metal, a Group 13 element, a Group 14 element, a transition metal, a rare earth element, or a combination thereof, not Sn), etc.
- Element Y' is, for example, 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, Ti, Ge, P, As, Sb, Bi, S, Se, Te, Po, or combinations thereof.
- the transition metal oxide is, for example, lithium titanium oxide, vanadium oxide, lithium vanadium oxide and the like.
- the non-transition metal oxide is, for example, SnO 2 , SiO x (0 ⁇ x ⁇ 2), and the like.
- the carbon-based material is, for example, crystalline carbon, amorphous carbon or a mixture thereof.
- the crystalline carbon is, for example, graphite such as natural graphite or artificial graphite in amorphous, platy, flake, spherical or fibrous form.
- the amorphous carbon is, for example, soft carbon (low-temperature calcined carbon) or hard carbon, mesophase pitch carbide, calcined coke, and the like.
- the contents of the negative electrode active material, conductive agent, binder, and solvent are levels commonly used in lithium secondary batteries. Depending on the use and configuration of the lithium secondary battery, one or more of the conductive material, binder, and solvent may be omitted.
- any separator commonly used in a lithium secondary battery may be used.
- An electrolyte having a low resistance to ion movement and excellent electrolyte moisture absorption ability may be used.
- it may be selected from glass fibers, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE), or combinations thereof, and may be in the form of non-woven fabric or woven fabric.
- PTFE polytetrafluoroethylene
- a rollable separator such as polyethylene or polypropylene may be used in a lithium ion battery, and a separator having excellent electrolyte impregnating ability may be used in a lithium ion polymer battery.
- the separator may be manufactured according to the following method.
- a separator composition is prepared by mixing a polymer resin, a filler, and a solvent.
- a separator may be formed by directly coating and drying the separator composition on an electrode. Alternatively, after the separator composition is cast and dried on a support, a separator film separated from the support may be laminated on an electrode to form a separator.
- the polymer resin used to manufacture the separator is not particularly limited, and all materials used for the binder of the electrode plate may be used.
- vinylidene fluoride/hexafluoropropylene copolymer polyvinylidene fluoride (PVDF), polyacrylonitrile, polymethyl methacrylate, or mixtures thereof may be used.
- PVDF polyvinylidene fluoride
- the electrolyte may further include an organic solid electrolyte and/or an inorganic solid electrolyte in addition to the above-described electrolyte.
- polyethylene derivatives polyethylene oxide derivatives, polypropylene oxide derivatives, phosphoric acid ester polymers, polyester sulfide, polyvinyl alcohol, polyvinylidene fluoride, and the like may be used as the organic solid electrolyte.
- the inorganic solid electrolyte is not limited to boron oxide, lithium oxynitride, etc., and any solid electrolyte used in the art is possible.
- the inorganic solid electrolyte is formed on the negative electrode by, for example, sputtering, or a separate solid electrolyte sheet is laminated on the negative electrode.
- a lithium secondary battery 1 includes a positive electrode 3 , a negative electrode 2 and a separator 4 .
- the positive electrode 3, the negative electrode 2, and the separator 4 are wound or folded and accommodated in the battery case 5.
- Electrolyte is injected into the battery case 5 and sealed with a cap assembly 6 to complete the lithium secondary battery 1 .
- the battery case 5 is cylindrical, but not necessarily limited to this shape, for example, a prismatic shape, a thin film shape, a coin shape, and the like.
- a pouch-type lithium secondary battery includes one or more battery structures.
- a separator is disposed between the positive electrode and the negative electrode to form a battery structure.
- the battery structure is stacked in a bi-cell structure, it is impregnated with an organic electrolyte, accommodated in a pouch, and sealed to complete a pouch-type lithium secondary battery.
- a plurality of battery structures are stacked to form a battery pack, and the battery pack is used in all devices requiring high capacity and high output. For example, it is used in notebooks, smartphones, and electric vehicles.
- Lithium secondary batteries have excellent lifespan characteristics and high rate characteristics, so they are used, for example, in electric vehicles (EVs). For example, it is used for hybrid vehicles such as plug-in hybrid electric vehicles (PHEVs). It is also used in fields requiring large amounts of power storage. For example, it is used for electric bicycles, power tools, etc.
- EVs electric vehicles
- PHEVs plug-in hybrid electric vehicles
- PHEVs plug-in hybrid electric vehicles
- power storage For example, it is used for electric bicycles, power tools, etc.
- a and b of "carbon number a to b" mean the carbon number of a specific functional group. That is, the functional group may include carbon atoms from a to b.
- an alkyl group having 1 to 4 carbon atoms refers to an alkyl group having 1 to 4 carbon atoms, that is, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 -, CH 3 CH 2 CH(CH 3 )- and (CH 3 ) 3 C-.
- radicals may include mono-radical or di-radical, depending on the context.
- substituents specified as alkyl groups requiring two linking points include diradicals such as -CH 2 -, -CH 2 CH 2 -, -CH 2 CH(CH 3 )CH 2 -, and the like.
- Other radical nomenclatures such as "alkylene" clearly indicate that the radical is a diradical.
- alkyl group refers to a branched or unbranched aliphatic hydrocarbon group.
- an alkyl group can be substituted or unsubstituted.
- the alkyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, etc.
- the alkyl group may have 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms may be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec-butyl, pentyl, 3-pentyl, hexyl, etc., but is not necessarily limited thereto.
- cycloalkyl group refers to a fully saturated carbocyclic ring or ring system.
- cyclopropyl cyclobutyl
- cyclopentyl cyclohexyl
- alkenyl group is a hydrocarbon group containing 2 to 20 carbon atoms including at least one carbon-carbon double bond, and includes ethenyl group, 1-propenyl group, 2-propenyl group, 2-methyl- 1-propenyl group, 1-butenyl group, 2-butenyl group, cyclopropenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, and the like, but are not limited thereto.
- an alkenyl group can be substituted or unsubstituted.
- an alkenyl group can have 2 to 40 carbon atoms.
- alkynyl group is a hydrocarbon group containing 2 to 20 carbon atoms including at least one carbon-carbon triple bond, and includes an ethynyl group, 1-propynyl group, 1-butynyl group, and 2-butynyl group. Including, but not limited to, and the like.
- an alkynyl group can be substituted or unsubstituted.
- an alkynyl group can have 2 to 40 carbon atoms.
- alkoxy group refers to an alkyl group bonded to oxygen, and specific examples of the alkoxy group include methoxy, ethoxy, propoxy, and the like, and one or more hydrogen atoms of the alkoxy group are It may be substituted or unsubstituted.
- aromatic means a ring or ring system having a conjugated pi electron system, and includes carbocyclic aromatic groups (eg, phenyl groups) and heterocyclic aromatic groups (eg, pyridine).
- carbocyclic aromatic groups eg, phenyl groups
- heterocyclic aromatic groups eg, pyridine.
- the term includes monocyclic or fused polycyclic rings (ie, rings that share adjacent pairs of atoms), provided that the entire ring system is aromatic.
- aryl group refers to an aromatic ring or ring system in which the ring backbone contains only carbon (ie, two or more fused rings sharing two adjacent carbon atoms).
- the aryl group is a ring system, each ring in the system is aromatic.
- the aryl group includes, but is not limited to, a phenyl group, a biphenyl group, a naphthyl group, a phenanthrenyl group, a naphthacenyl group, and the like.
- the aryl group may be substituted or unsubstituted.
- heteroaryl group refers to an aromatic ring system having one ring or a plurality of fused rings, wherein at least one ring atom is not carbon, i.e., a heteroatom.
- fused ring systems one or more heteroatoms can be present in only one ring.
- heteroatoms include, but are not necessarily limited to, oxygen, sulfur and nitrogen.
- heteroaryl groups include furanyl, thienyl, imidazolyl, quinazolinyl, quinolinyl, isoquinolinyl, and quinox. It may be a quinoxalinyl group, a pyridinyl group, a pyrrolyl group, an oxazolyl group, an indolyl group, or the like, but is not limited thereto.
- aralkyl group and “alkylaryl group” refer to an aryl group connected as a substituent via an alkylene group, such as an aralkyl group having 7 to 14 carbon atoms, etc., and includes benzyl, 2-phenylethyl, 3- It includes, but is not limited to, a phenylpropyl group and a naphthylalkyl group.
- the alkylene group is a lower alkylene group (ie, an alkylene group having 1 to 4 carbon atoms).
- aryloxy group refers to an aryl group bonded to oxygen, and specific examples of the aryloxy group include phenoxy and the like, and one or more hydrogen atoms of the aryl group may or may not be substituted. may not be
- a "cycloalkenyl group” is a carbocytyl ring or ring system having one or more double bonds, and is a ring system without an aromatic ring.
- a cyclohexenyl group is a carbocytyl ring or ring system having one or more double bonds, and is a ring system without an aromatic ring.
- heterocyclyl group is a non-aromatic ring or ring system containing one or more heteroatoms in the ring skeleton.
- halogen is a stable element belonging to group 17 of the periodic table of elements, for example, fluorine, chlorine, bromine or iodine, and particularly fluorine and/or chlorine.
- cyano group means "-CN group”.
- substituents are derived by exchanging one or more hydrogen atoms or functional groups in an unsubstituted parent group.
- a functional group when a functional group is considered “substituted”, it means that the functional group is an alkyl group of 1 to 40 carbon atoms, an alkenyl group of 2 to 40 carbon atoms, a cycloalkyl group of 3 to 40 carbon atoms, a cycloalkyl group of 3 to 40 carbon atoms It means that it is substituted with one or more substituents selected from an alkenyl group, an alkyl group having 1 to 40 carbon atoms, and an aryl group having 7 to 40 carbon atoms.
- a functional group is described as “optionally substituted”, it is meant that the functional group may be substituted with the substituents described above.
- Example 1 1 part by weight of Compound 1 and 1 part by weight of Compound 3
- LiPF 6 LiPF 6 was added to a mixed solvent of ethylene carbonate (EC), propylene carbonate (PC), ethyl propionate (EP), and propyl propionate (PP) in a volume ratio of 10:15:30:45. .
- Example 2 1.5 parts by weight of Compound 1 and 1.5 parts by weight of Compound 3
- Example 3 0.3 parts by weight of Compound 1 and 0.3 parts by weight of Compound 3
- Example 4 1 part by weight of compound 1 and 2 parts by weight of compound 3
- Example 5 1 part by weight of Compound 1 and 3 parts by weight of Compound 3
- Example 6 1 part by weight of Compound 1 and 7 parts by weight of Compound 3
- Example 7 7 parts by weight of Compound 1 and 1 part by weight of Compound 3
- LiPF 6 1.3 M LiPF 6 was added to a mixed solvent in which the volume ratio of ethylene carbonate (EC), propylene carbonate (PC), ethyl propionate (EP), and propyl propionate (PP) was 10:15:30:45. Electrolyte was prepared.
- Example 1 except that 2 parts by weight of dimethoxy diphenyl silane (manufactured by Sigma Aldrich, 'Compound 3') was added to the mixed solvent as a silane-based compound additive based on 100 parts by weight of the total electrolyte.
- An electrolyte was prepared in the same manner as in
- Example 1 except that 2 parts by weight of diethoxy diphenyl silane (manufactured by Sigma Aldrich, 'Compound 4') was added to the mixed solvent as a silane-based compound additive based on 100 parts by weight of the total electrolyte.
- An electrolyte was prepared in the same manner as in
- Comparative Example 5 8 parts by weight of Compound 1 and 8 parts by weight of Compound 3
- LiCoO 2 LiCoO 2
- artificial graphite powder 0.5% by weight of artificial graphite powder as a conductive material
- carbon black 0.8% by weight of carbon black (Ketjenblack)
- acrylonitrile rubber 0.2% by weight of acrylonitrile rubber
- PVdF polyvinylidene fluoride
- a lithium secondary battery (coin cell) was manufactured using a polyethylene separator having a thickness of 14 ⁇ m in which a positive electrode was coated with ceramic as a separator and the electrolyte prepared in Example 1 as an electrolyte.
- a lithium secondary battery (coin cell) was manufactured in the same manner as in Example 8, except that the electrolyte prepared in Examples 2 to 7 was used instead of the electrolyte prepared in Example 1.
- a lithium secondary battery (coin cell) was manufactured in the same manner as in Example 8, except that the electrolyte prepared in Comparative Examples 1 to 5 was used instead of the electrolyte prepared in Example 1.
- a positive electrode was prepared according to the following procedure.
- a lithium secondary battery (a pouch cell of about 40 mAh) was manufactured using a polyethylene separator (thickness: 16 ⁇ m) as a separator and the electrolyte of Example 1 as an electrolyte.
- a lithium secondary battery (pouch cell) was manufactured in the same manner as in Example 15, except that the electrolyte prepared in Examples 2 to 7 was used instead of the electrolyte prepared in Example 1.
- a lithium secondary battery (pouch cell) was manufactured in the same manner as in Example 15, except that the electrolyte prepared in Comparative Examples 1 to 5 was used instead of the electrolyte prepared in Example 1.
- the lithium secondary batteries prepared in Examples 8 to 9 and Comparative Examples 6 to 10 were subjected to a formation step, and the voltage of the lithium secondary batteries that had undergone the formation step was 6 V (vs. Li) was charged until it reached, and the arrival time was calculated.
- the results are shown in Table 1 and FIG. 2 below.
- the lithium secondary battery prepared in Examples 8 to 9 (using 1 part by weight and 1.5 parts by weight of additive compound 1 and compound 3 in the electrolyte, respectively) was compared to Comparative Examples 6 to 10 (electrolyte It can be seen that the voltage increase rate is the most delayed compared to the lithium secondary battery prepared by using 2 parts by weight of additive compound 1, compound 3, or compound 4 alone, using 8 parts by weight of compound 1 and 8 parts by weight of compound 3). there is.
- first cell two cells (hereinafter referred to as “first cell” and “second cell”) of each of the lithium secondary batteries prepared by Examples 15 to 21 and Comparative Examples 11, 12, 13, and 15 were chemically formed at 25 ° C.
- the state of the lithium secondary battery was observed while charging the lithium secondary battery that had undergone the formation step at a current of 0.2 C rate for 7 hours and 30 minutes at a constant current until the voltage reached 10 V (vs. Li).
- the experimental results were indicated as NG (NOT GOOD) and OK, and the maximum temperature (°C) of the first cell and the second cell and the short occurrence time of the first cell and the second cell were recorded.
- the results are shown in Table 2 below.
- Lithium secondary batteries prepared in Examples 15 to 21 were lithium secondary batteries prepared in Comparative Examples 11, 12, and 13 (no additives in the electrolyte, additive compound 1 in the electrolyte) or using compound 3), the maximum temperature in the overcharge step was low and there was no short circuit.
- the lithium secondary batteries manufactured by Examples 15 to 21 and Comparative Examples 12, 13, 15, and 17 were subjected to a conversion step at 25 ° C, and the lithium secondary batteries that had undergone the conversion step were subjected to a current of 1.5 C rate at 25 ° C. Constant current charging until the voltage reached 4.48 V (vs. Li), and cut-off at a current of 0.02 C rate while maintaining 4.48 V in constant voltage mode. Subsequently, after storage at 25 ° C and -10 ° C for 2 hours, the cell was discharged at a constant current of 0.2 C rate until the voltage reached 3.0 V (vs. Li) at 25 ° C and -10 ° C, respectively. each prepared.
- the discharge capacity for each temperature (25 °C, -10 °C) of the prepared cell was measured.
- the discharge capacity at each measured temperature (25 °C, -10 °C) was substituted into the following formula 1 to obtain the low temperature (-10 °C) discharge capacity ratio (%).
- the results are shown in Table 3 below.
- the low temperature (-10 °C) discharge capacity ratio of the lithium secondary battery prepared by Examples 15 to 21 Comparative Examples 11, 12, 13, 15 (no additives in the electrolyte, additive compound 1 2 in the electrolyte) parts by weight, 2 parts by weight of Compound 3, and 8 parts by weight of Compound 1 and 8 parts by weight of Compound 3) were similar to or higher than those of the lithium secondary battery manufactured.
- the lithium secondary battery prepared in Example 17 (using 0.3 parts by weight of additive compound 1 and 0.3 parts by weight of compound 3 in the electrolyte) had the highest low-temperature (-10 ° C) discharge capacity ratio.
- Comparative Example 15 contained a sulfone-based compound having at least one phenyl group and a silane-based compound having at least one phenyl group at a ratio of 1:1, but the low-temperature discharge capacity ratio was the lowest at 16 parts by weight, which is 10 parts by weight or more in the sum of the two compounds.
- the lithium secondary batteries prepared in Examples 15 to 21 can improve safety by improving overcharge characteristics without lowering the discharge capacity ratio at low temperature (-10 ° C) even when sulfone-based compound additives and silane-based compound additives are used in the electrolyte. It can be seen that there is
- the lithium secondary batteries manufactured in Examples 15 to 21 and Comparative Examples 12, 13, 15, and 17 were subjected to a conversion step at 25 ° C, and the lithium secondary batteries that had undergone the conversion step were subjected to a current of 1.5 C rate at 25 ° C. Constant current charging until the voltage reached 4.48 V (vs. Li), and cut-off at a current of 0.02 C rate while maintaining 4.48 V in constant voltage mode. Subsequently, the lithium secondary battery was stored at 60 °C for 8 weeks. The cell thickness before storage was measured, and the cell thickness was measured after 8 weeks of storage, respectively. The thickness increase rate was obtained by substituting the measured battery thickness before storage and after storage for 8 weeks into Equation 2 below. The results are shown in Table 4 below.
- the high-temperature storage thickness increase rate of the lithium secondary battery prepared by Examples 15 to 21 is Comparative Examples 11, 12, 13, and 15 (no additives in the electrolyte, 2 parts by weight of the additive compound 1 in the electrolyte, the compound 3, 2 parts by weight, and 8 parts by weight of Compound 1 and 8 parts by weight of Compound 3) were slightly higher or lower than those of the lithium secondary battery manufactured. Additives using 0.3 parts by weight of Compound 1 and 0.3 parts by weight of Compound 3) had the lowest high-temperature storage thickness increase rate.
- Comparative Example 15 contained a sulfone-based compound having at least one phenyl group and a silane-based compound having at least one phenyl group at a ratio of 1:1, but the thickness increase rate was high at 16 parts by weight, which is 10 parts by weight or more in the sum of the two compounds.
- the lithium secondary batteries prepared in Examples 15 to 21 can improve safety by improving overcharge characteristics without increasing the thickness increase rate at high temperature (60 ° C) even when sulfone-based compound additives and silane-based compound additives are used in the electrolyte. It can be seen that there is
- the lithium secondary batteries manufactured in Examples 15 to 21 and Comparative Examples 11, 12, 13, and 15 were subjected to a conversion step at 25 ° C, and the lithium secondary batteries that had undergone the conversion step were subjected to a current of 1.5 C rate at 45 ° C. Constant current charging was performed until the voltage reached 4.48 V (vs. Li), followed by cut-off at a current of 0.05 C rate while maintaining 4.48 V in constant voltage mode. Subsequently, the discharge was performed at a constant current of 0.5 C rate until the voltage reached 3.0 V (vs. Li). This charge/discharge cycle was repeated 300 times. In all the above charge/discharge cycles, a stop time of 10 minutes was set after one charge/discharge cycle. The results are shown in Table 5 below. The capacity retention rate at 300 th cycle is defined by Equation 3 below.
- Example 15 92.8
- Example 16 92.1
- Example 17 93.2
- Example 18 91.0
- Example 19 92.6
- Example 20 89.7
- Example 21 88.1 Comparative Example 11 87.4 Comparative Example 12 87.9 Comparative Example 13 86.9 Comparative Example 15 83.2
- the high temperature (45 °C) capacity retention rate of the lithium secondary battery prepared by Examples 15 to 21 is Comparative Examples 11, 12, 13, and 15 (no additives in the electrolyte, 2 weights of additive compound 1 in the electrolyte) parts, 2 parts by weight of Compound 3, and 8 parts by weight of Compound 1 and 8 parts by weight of Compound 3) were similar or higher than those of the lithium secondary battery manufactured.
- the lithium secondary battery prepared in Example 17 (using 0.3 parts by weight of additive compound 1 and 0.3 parts by weight of compound 3 in the electrolyte) had the highest capacity retention rate at high temperature (45 °C).
- the lithium secondary batteries prepared in Examples 15 to 21 can improve safety by improving overcharge characteristics without deterioration in capacity retention rate at high temperature (45 ° C) even when sulfone-based compound additives and silane-based compound additives are used in the electrolyte. can know
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Abstract
Description
구분 | 6V 전압에 이를 때까지 시간(초) |
실시예 8 | 7970 |
실시예 9 | 8390 |
비교예 6 | 3579 |
비교예 7 | 6756 |
비교예 8 | 4300 |
비교예 9 | 6415 |
비교예 10 | 4576 |
구분 | 과충전 결과 | 제1셀 /제2셀 최대온도(℃) |
제1셀/제2셀 단락(short) 발생시간 |
실시예 15 | OK | 41.2/77.1 | - |
실시예 16 | OK | 67.2/44.9 | - |
실시예 17 | OK | 71.8/83.4 | - |
실시예 18 | OK | 73.6/32.5 | - |
실시예 19 | OK | 56.3/69.2 | - |
실시예 20 | OK | 74.7/79.6 | - |
실시예 21 | OK | 73.8/52.9 | - |
비교예 11 | NG | 452/428 | 2시간 58분/2시간 53분 |
비교예 12 | NG | 286/303 | 5시간 12분/5시간 24분 |
비교예 13 | NG | 265/242 | 4시간 56분/4시간 37분 |
비교예 15 | OK | 78.1/67.5 | - |
구분 | 저온(-10 ℃) 방전용량비(%) |
실시예 15 | 85.1 |
실시예 16 | 86.7 |
실시예 17 | 87.9 |
실시예 18 | 83.5 |
실시예 19 | 85.3 |
실시예 20 | 82.4 |
실시예 21 | 83.6 |
비교예 11 | 82.1 |
비교예 12 | 83.1 |
비교예 13 | 84.9 |
비교예 15 | 73.2 |
구분 | 고온(60℃) 저장 두께 증가율(%) |
실시예 15 | 9.15 |
실시예 16 | 9.01 |
실시예 17 | 8.82 |
실시예 18 | 9.36 |
실시예 19 | 9.24 |
실시예 20 | 9.67 |
실시예 21 | 9.43 |
비교예 11 | 9.75 |
비교예 12 | 9.51 |
비교예 13 | 9.45 |
비교예 15 | 14.8 |
구분 | 고온(45℃) 용량유지율(%) |
실시예 15 | 92.8 |
실시예 16 | 92.1 |
실시예 17 | 93.2 |
실시예 18 | 91.0 |
실시예 19 | 92.6 |
실시예 20 | 89.7 |
실시예 21 | 88.1 |
비교예 11 | 87.4 |
비교예 12 | 87.9 |
비교예 13 | 86.9 |
비교예 15 | 83.2 |
Claims (9)
- 리튬염;비수계 유기용매; 및하나 이상의 페닐기를 갖는 설폰계 화합물 첨가제 및 하나 이상의 페닐기를 갖는 실란계 화합물 첨가제;를 포함하는, 리튬이차전지용 전해질.
- 제1 항에 있어서,상기 설폰계 화합물 첨가제는 하기 화학식 1로 표시되는 화합물인, 리튬이차전지용 전해질:[화학식 1]식 중,R1, R2는 서로 독립적으로 치환 또는 비치환된 C1-C10 알킬기, 치환 또는 비치환된 C2-C10 알케닐기, 치환 또는 비치환된 C3-C10 알키닐기, 치환 또는 비치환된 C3-C20 시클로알킬기, 치환 또는 비치환된 C6-C50 아릴기, 치환 또는 비치환된 C6-C50 알킬아릴기, 또는 치환 또는 비치환된 C6-C50 헤테로아릴기이되,상기 R1, R2 중 적어도 하나는 할로겐 원소로 치환 또는 비치환된 C6 아릴기이다.
- 제1 항에 있어서,상기 설폰계 화합물 첨가제는 하기 화학식 1-1로 표시되는 화합물을 포함하는, 리튬이차전지용 전해질:[화학식 1-1]식 중,R'1, R'2, R'3, R'4, R'5, R'6, R'7, R'8, R'9, R'10은 서로 독립적으로 수소원자, 할로겐원자, 시아노기, -ORa(Ra은 C1-C10의 알킬기, 또는 C6-C20의 아릴기이다), -C(=O)Rb, -C(=O)ORb, -OCO(ORb), -(X)n-NH2(X는 C1-C10의 알킬기, 또는 C1-C10의 알콕시기이고, n은 0 내지 10의 정수이다), -C=N(Rb), -SRb, -S(=O)Rb, -S(=O)2Rb, 치환 또는 비치환된 C1-C20의 알킬기, 치환 또는 비치환된 C1-C20의 알콕시기, 치환 또는 비치환된 C2-C20의 알케닐기, 치환 또는 비치환된 C2-C20의 알키닐기, 치환 또는 비치환된 C3-C30의 시클로알킬기, 치환 또는 비치환된 C6-C30의 아릴기, 치환 또는 비치환된 C6-C30의 아릴옥시기, 또는 치환 또는 비치환된 C6-C30의 헤테로아릴기이고, 여기서 Rb는 수소, C1-C10의 알킬기, 또는 C6-C20의 아릴기이되,상기 R'1, R'2, R'3, R'4, R'5, R'6, R'7, R'8, R'9, R'10 중 적어도 하나는 불소원자이다.
- 제1 항에 있어서,상기 실란계 화합물 첨가제는 하기 화학식 2로 표시되는 화합물인, 리튬이차전지용 전해질:[화학식 2]식 중,R3, R4, R5, R6은 서로 독립적으로 -OR'a(R'a는 C1-C10의 알킬기, 또는 C6-C20의 아릴기이다), C(=O)R'b, -C(=O)OR'b, 치환 또는 비치환된 C1-C10 알킬기, 치환 또는 비치환된 C2-C10 알케닐기, 치환 또는 비치환된 C3-C10 알키닐기, 치환 또는 비치환된 C3-C20 시클로알킬기, 치환 또는 비치환된 C6-C50 아릴기, 치환 또는 비치환된 C6-C50의 아릴옥시기, 치환 또는 비치환된 C6-C50 알킬아릴기, 또는 치환 또는 비치환된 C6-C50 헤테로아릴기이고, 여기서 R'b는 수소, C1-C10의 알킬기, 또는 C6-C20의 아릴기이되,상기 R3, R4, R5, R6 중 적어도 하나는 치환 또는 비치환된 C6 아릴기이다.
- 제1 항에 있어서,상기 실란계 화합물 첨가제는 하기 화학식 2-1로 표시되는 화합물을 포함하는, 리튬이차전지용 전해질:[화학식 2-1]식 중,R'11, R'12는 서로 독립적으로 C(=O)R"a, -C(=O)OR"a, 치환 또는 비치환된 C1-C10 알킬기, 치환 또는 비치환된 C2-C10 알케닐기, 치환 또는 비치환된 C3-C10 알키닐기, 치환 또는 비치환된 C3-C20 시클로알킬기, 치환 또는 비치환된 C6-C30 아릴기, 치환 또는 비치환된 C6-C30 알킬아릴기, 또는 치환 또는 비치환된 C6-C30 헤테로아릴기이고, 여기서 R"a는 수소, C1-C10의 알킬기, 또는 C6-C20의 아릴기이다.
- 제1 항에 있어서,상기 설폰계 화합물 첨가제와 상기 실란계 화합물 첨가제의 중량비가 1:7 내지 7:1인, 리튬이차전지용 전해질.
- 제1 항에 있어서,상기 설폰계 화합물 첨가제 및 상기 실란계 화합물 첨가제의 총 함량이 전해질 전체 100 중량부를 기준으로 하여 0.1 내지 10 중량부인, 리튬이차전지용 전해질.
- 양극 활물질을 포함하는 양극;음극 활물질을 포함하는 음극; 및상기 양극과 음극 사이에 배치된 제1항 내지 제8항 중 어느 한 항에 따른 전해질;을 포함하는 리튬이차전지.
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US20030003370A1 (en) * | 2001-05-15 | 2003-01-02 | Juichi Arai | Lithium secondary battery |
KR20190024104A (ko) * | 2017-08-31 | 2019-03-08 | (주)코이즈 | 이차전지용 전해액, 이를 포함하는 리튬 이차전지 또는 하이브리드 캐패시터 |
KR20200099883A (ko) * | 2019-02-15 | 2020-08-25 | 주식회사 유뱃 | 전기화학 소자 및 이의 제조방법 |
KR20200102613A (ko) * | 2019-02-21 | 2020-09-01 | 주식회사 유뱃 | 전기화학 소자 및 이의 제조방법 |
-
2021
- 2021-06-16 KR KR1020210078056A patent/KR20220168389A/ko unknown
-
2022
- 2022-05-28 EP EP22825185.6A patent/EP4358217A1/en active Pending
- 2022-05-28 WO PCT/KR2022/007616 patent/WO2022265259A1/ko active Application Filing
- 2022-05-28 US US18/003,860 patent/US20230327199A1/en active Pending
- 2022-05-28 CN CN202280042307.0A patent/CN117480656A/zh active Pending
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US20030003370A1 (en) * | 2001-05-15 | 2003-01-02 | Juichi Arai | Lithium secondary battery |
KR20190024104A (ko) * | 2017-08-31 | 2019-03-08 | (주)코이즈 | 이차전지용 전해액, 이를 포함하는 리튬 이차전지 또는 하이브리드 캐패시터 |
KR20200099883A (ko) * | 2019-02-15 | 2020-08-25 | 주식회사 유뱃 | 전기화학 소자 및 이의 제조방법 |
KR20200102613A (ko) * | 2019-02-21 | 2020-09-01 | 주식회사 유뱃 | 전기화학 소자 및 이의 제조방법 |
Non-Patent Citations (1)
Title |
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CHEN LANG; XU MENGQING; LI BIN; XING LIDAN; WANG YONG; LI WEISHAN: "Dimethoxydiphenylsilane (DDS) as overcharge protection additive for lithium-ion batteries", JOURNAL OF POWER SOURCES, vol. 244, 2 April 2013 (2013-04-02), AMSTERDAM, NL, pages 499 - 504, XP028692091, ISSN: 0378-7753, DOI: 10.1016/j.jpowsour.2013.03.139 * |
Also Published As
Publication number | Publication date |
---|---|
CN117480656A (zh) | 2024-01-30 |
KR20220168389A (ko) | 2022-12-23 |
EP4358217A1 (en) | 2024-04-24 |
US20230327199A1 (en) | 2023-10-12 |
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