WO2022010227A1 - Additif pour électrolyte destiné à une batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant - Google Patents

Additif pour électrolyte destiné à une batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant Download PDF

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Publication number
WO2022010227A1
WO2022010227A1 PCT/KR2021/008573 KR2021008573W WO2022010227A1 WO 2022010227 A1 WO2022010227 A1 WO 2022010227A1 KR 2021008573 W KR2021008573 W KR 2021008573W WO 2022010227 A1 WO2022010227 A1 WO 2022010227A1
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Prior art keywords
formula
electrolyte
secondary battery
lithium
additive
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PCT/KR2021/008573
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English (en)
Korean (ko)
Inventor
백용구
양원기
김동원
박성준
Original Assignee
주식회사 테크늄
백용구
얍엑스 주식회사
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Publication of WO2022010227A1 publication Critical patent/WO2022010227A1/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
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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 for a lithium secondary battery, an electrolyte including the same, and a lithium secondary battery.
  • the charging and driving voltage of the battery can be improved, and a silicon-based material rather than a carbon-based material is used as the negative electrode active material. Because it can be used as a battery, the capacity of the battery can be improved.
  • lithium salt dissolved in a solvent is used as an electrolyte.
  • the over-lithium positive electrode active material creates a high voltage environment while generating oxygen gas during the first charge, and the silicon-based negative electrode active material is subjected to repeated charging and discharging. Severe volume expansion occurs and cracks are formed on the surface, and eventually, electrolyte decomposition reaction is commonly induced on the surface of the electrode to which each active material is applied.
  • the electrolyte is gradually depleted, and the electrochemical performance of the battery is rapidly deteriorated, and as a thick film acting as a resistance is formed on the surface of each electrode, the electrochemical reaction rate of the battery is lowered.
  • an acidic material eg, HF, etc.
  • additives such as 1,3-propanesultone and 1,3-propensultone, which have been extensively studied as electrolyte additives in the prior art, improve high-temperature storage characteristics of secondary batteries during long-term high-temperature storage, but high-temperature lifespan characteristics of secondary batteries. This diminishing problem arises.
  • the present invention is to solve the problem of cell swelling by adding a special additive to an electrolyte for a lithium secondary battery so that a by-product generated by reacting with HF becomes a liquid at room temperature.
  • an object of the present invention to provide an electrolyte additive having a function of efficiently removing HF in a secondary battery with a small amount of equivalent, and forming a passivation film on the surface of the anode as the produced material acts as a reductive decomposition additive.
  • an object of the present invention is to provide an electrolyte additive that can be efficiently applied to a perlithium positive electrode active material and a silicon-based negative electrode active material.
  • the electrolyte additive for a secondary battery according to an embodiment of the present invention includes a compound represented by the following formula (1).
  • R1, R2, R3 and R4 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a C1-C6 alkenyl group, and a C1-C6 alkyl group. a nyl group or a C6-C10 aryl group, wherein R5 is a substituted or unsubstituted C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, or C6-C10 aryl group).
  • the electrolyte additive for a secondary battery according to an embodiment of the present invention may include at least one material selected from the following Chemical Formulas 1-1 to 1-9.
  • the electrolyte additive for a secondary battery according to an embodiment of the present invention may react with HF in a lithium secondary battery to form a compound represented by the following formula (2).
  • R1, R2, R3 and R4 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a C1-C6 alkenyl group, and a C1-C6 alkyl group. a nyl group or a C6-C10 aryl group, wherein R5 is a substituted or unsubstituted C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, or C6-C10 aryl group).
  • the compound represented by Formula 2 may be in a liquid state at room temperature (25° C.).
  • the electrolyte for a secondary battery includes an electrolyte additive for a secondary battery represented by Chemical Formula 1; lithium salt; and a solvent;
  • the electrolyte for a secondary battery according to an embodiment of the present invention may further include an oxidative decomposition type additive.
  • the electrolyte additive for a secondary battery represented by Formula 1 may be included in an amount of 0.01 to 10% by weight based on the total weight of the electrolyte.
  • a secondary battery includes a positive electrode; cathode; a separator interposed between the anode and the cathode; and an electrolyte for the secondary battery.
  • the positive electrode of the secondary battery according to an embodiment of the present invention may include a lithium-rich positive electrode active material.
  • the negative electrode of the secondary battery according to an embodiment of the present invention may include a silicon negative electrode active material.
  • An object of the present invention is to solve the problem of cell swelling by allowing the by-product generated by reacting with the electrolyte HF for a secondary battery according to an embodiment of the present invention to become a liquid at room temperature.
  • the electrolyte additive for a secondary battery can efficiently remove HF in a secondary battery with a small equivalent, and at the same time, the produced material acts as a reductive decomposition type additive to form a passivation film on the surface of the anode.
  • the electrolyte additive for a secondary battery by applying the electrolyte additive for a secondary battery to a secondary battery, the electrochemical performance, reaction rate, and stability of the battery can be improved.
  • the electrolyte additive for a secondary battery according to an embodiment of the present invention includes a compound represented by the following formula (1).
  • R1, R2, R3 and R4 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a C1-C6 alkenyl group, and a C1-C6 alkynyl group. , or a C6-C10 aryl group, wherein R5 is a substituted or unsubstituted C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, or C6-C10 aryl group.
  • the electrolyte additive represented by Chemical Formula 1 may be purchased or manufactured, and the place of purchase or a manufacturing method thereof is not particularly limited.
  • the electrolyte additive may be at least one material selected from the following Chemical Formulas 1-1 to 1-9.
  • the electrolyte additive may react with HF in the lithium secondary battery to form a compound represented by the following formula (2).
  • R1, R2, R3 and R4 are the same as or different from each other, and each independently represents hydrogen, a substituted or unsubstituted C1-C6 alkyl group, a C1-C6 alkenyl group, and a C1-C6 alkynyl group. , or a C6-C10 aryl group, wherein R5 is a substituted or unsubstituted C1-C6 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, or C6-C10 aryl group.
  • the mechanism of generating HF in the lithium secondary battery and the mechanism in which the electrolyte additive represented by Formula 1 reacts with HF in the lithium secondary battery to form the compound represented by Formula 2 are as follows.
  • the thickness of the battery expands during charging.
  • the negative electrode passivation film is gradually collapsed by the increased electrochemical energy and thermal energy over time, and a side reaction in which the surrounding electrolyte reacts with the newly exposed surface of the negative electrode continues to occur.
  • the internal pressure of the secondary battery increases, and performance degradation occurs such as a decrease in the lifespan of the secondary battery at a high temperature due to volume expansion of the secondary battery.
  • the electrolyte additive according to an embodiment of the present invention can suppress the shortening of the battery life by removing HF generated by moisture as in the above mechanism.
  • the compound represented by Formula 2 generated by the reaction of the electrolyte additive with HF may be in a liquid state at room temperature (25° C.).
  • the existing HF skivenzer has a problem in that the cell swells due to the formation of gas due to the low boiling point of the generated by-product.
  • the present invention can solve the problem of cell swelling by generating a by-product in a liquid state.
  • the electrolyte additive may form a solid electrolyte interphase (SEI) on the surface of the anode by removing the HF and simultaneously forming a compound represented by Chemical Formula 2 as a reductive decomposition additive.
  • SEIs have ion conductivity and serve to help lithium ions move.
  • due to the passivation film generated by the electrolyte additive it is possible to suppress the further decomposition of the electrolyte and improve the reversible capacity.
  • the additive according to the embodiment of the present invention when applied to a lithium secondary battery, the electrochemical performance, reaction rate and stability of the lithium secondary battery can be improved, and the capacity and lifespan maintenance rate can be sufficiently improved.
  • the lithium secondary battery electrolyte of the present invention is generally stable in a temperature range of -20 to 60 °C, and can maintain electrochemically stable characteristics even at a voltage of 4.5V, so it can be applied to all lithium secondary batteries such as lithium ion batteries and lithium polymer batteries. can
  • the electrolyte for a secondary battery includes an electrolyte additive for a secondary battery represented by Chemical Formula 1; lithium salt; and a solvent;
  • the electrolyte additive for a secondary battery represented by Chemical Formula 1 is the same as described above.
  • the electrolyte additive may be included in an amount of 0.01 to 10% by weight, or 0.01 to 5% by weight, or 0.01 to 3% by weight based on the total weight of the electrolyte.
  • the electrolyte additive is included in the above content, it is possible to form an appropriate amount of a passivation film formed on the surface of the negative electrode formed at the same time as removing HF in the secondary battery.
  • the lithium salt is preferably LiPF 6 , LiBF 4 , LiClO 4 , LiCl, LiBr, LiI, LiB 10 Cl 10 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, LiN(SO 2 C 2 F 5 ) 2 , Li(CF 3 SO 2 ) 2 N, LiC 4 F 9 SO 3 , LiB(C 6 H 5 ) 4 , Li(SO 2 F) 2 N(LiFSI) and (CF 3 SO 2 ) 2 NLi may be at least one selected from, but not particularly limited to.
  • the concentration of the lithium salt in the electrolyte of the present invention may be 0.1 to 2 M.
  • the solvent may be a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based, aprotic solvent, or a combination thereof.
  • the solvent is preferably ethylene carbonate (EC), ethyl methyl carbonate (EMC), dimethyl carbonate (dimethyl catbonate, DMC), diethyl carbonate (diethyl catbonate, DEC), Or it may be a combination thereof, but is not particularly limited thereto.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • the electrolyte for a secondary battery according to an embodiment of the present invention may further include an oxidative decomposition type additive.
  • the oxidative decomposition additive may be the following LiFOB, LiBOB, WCA1, WCA2, WCA3.
  • the electrolyte for a secondary battery according to an embodiment of the present invention may further include a reductive decomposition additive.
  • the reductive decomposition additive is selected from fluoroethylene carbonate (FEC) and vinylene carbonate (VC), propanesultone (PS), and propanylsultone (PRS) It may be at least any one or more.
  • the reductive decomposition additive may be included in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, more preferably 1 to 3% by weight relative to the total weight of the electrolyte.
  • the reductive decomposition additive is included in the above content, it is possible to prevent decomposition of the electrolyte and prevent damage to the negative electrode active material.
  • a secondary battery includes a positive electrode; cathode; a separator interposed between the anode and the cathode; and an electrolyte for the secondary battery.
  • the secondary battery may be a lithium secondary battery, and may be classified into a lithium ion battery, a lithium ion polymer battery, and a lithium polymer battery according to the type of a separator and an electrolyte.
  • the lithium secondary battery may be classified into a cylindrical shape, a prismatic shape, a coin type, a pouch type, etc. according to the shape, and may be divided into a bulk type and a thin film type according to the size.
  • the lithium secondary battery may have a form in which a negative electrode, a separator, and a positive electrode are sequentially stacked and then accommodated in a battery container while being wound on a spiral.
  • the positive electrode may include a current collector and a positive electrode active material layer formed on the current collector, and the positive electrode active material layer may include a positive electrode active material.
  • the cathode active material is a compound capable of reversible intercalation and deintercalation of lithium (lithiated intercalation compound), and any cathode active material available in the art may be used.
  • the positive electrode active material is a lithium-containing transition metal oxide, that is, lithium cobalt-based oxide, lithium manganese-based oxide, lithium copper oxide, lithium nickel-based oxide, lithium manganese composite oxide, and lithium-nickel-manganese-cobalt-based oxide. It may be at least any one or more selected from the group consisting of.
  • the positive electrode active material may include a lithium-rich positive electrode active material.
  • the positive electrode active material is a perlithium positive electrode active material, and may include a compound represented by the following formula (3).
  • the positive electrode active material layer may also include a binder and/or a conductive material.
  • the binder serves to well adhere the positive electrode active material particles to each other and the positive electrode active material to the current collector.
  • the conductive material serves to impart conductivity to the electrode.
  • any electronically conductive material that does not cause chemical change in the battery may be used.
  • metal powders such as natural graphite, artificial graphite, carbon black, acetylene black, Ketjen black, carbon fiber, copper, nickel, aluminum, silver, and metal fibers, metal fibers, etc. may be used, and conductive materials such as polyphenylene derivatives may be used alone or in combination of one or more.
  • the negative electrode may include a current collector and an anode active material layer formed on the current collector, and the anode active material layer may include an anode active material.
  • the negative active material is a material capable of reversibly intercalating and deintercalating lithium ions, and includes a carbon-based material, lithium metal, an alloy of lithium metal, a material capable of doping and de-doping lithium, a silicon-based or transition metal. oxides and the like can be used.
  • the carbon-based material includes crystalline carbon and amorphous carbon.
  • the crystalline carbon include graphite such as amorphous, plate-like, flake, spherical or fibrous natural graphite or artificial graphite, and examples of the amorphous carbon include soft carbon (low-temperature calcined carbon). or hard carbon, mesophase pitch carbide, and calcined coke.
  • the lithium metal alloy includes lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al and Sn from the group consisting of Alloys of metals of choice may be used.
  • silicon-based material a combination of graphite and silicon, a material in which silicon is coated on the surface of graphite particles, or a material in which silicon and carbon are simultaneously coated on the surface of graphite particles may be SiO x , Si may be carbon-based.
  • transition metal oxide examples include vanadium oxide and lithium vanadium oxide.
  • a carbon-based material such as graphite is widely known as a material capable of reversibly intercalating and deintercalating lithium ions.
  • Graphite has a low discharge voltage of -0.2V compared to lithium, and a battery using graphite as an anode active material exhibits a high discharge voltage of 3.6V, providing an advantage in terms of energy density of a lithium battery.
  • secondary batteries using graphite as an anode active material are the most widely used because they guarantee a long lifespan of lithium secondary batteries with excellent reversibility.
  • the graphite anode active material has a problem with low capacity in terms of energy density per unit volume of the electrode plate due to the low density of graphite (theoretical density 2.2 g/cc) during the manufacture of the electrode plate, and a side reaction with the organic electrolyte at a high discharge voltage is easy to occur, and the battery There is a problem of swelling and capacity degradation. Therefore, in recent years, as a material capable of doping and de-doping lithium, a silicon-based material having a high capacity has been in the spotlight as an alternative.
  • an electrolyte of a general lithium secondary battery a lithium salt dissolved in a solvent is used as an electrolyte.
  • the over-lithium positive electrode active material creates a high voltage environment while generating oxygen gas during the first charge, and the silicon-based negative electrode active material is repeatedly charged and discharged.
  • serious volume expansion occurs and cracks are formed on the surface, and eventually, a decomposition reaction of the electrolyte solution is commonly induced on the surface of the electrode to which each of the active materials is applied.
  • the electrolyte is gradually depleted, and the electrochemical performance of the battery is rapidly deteriorated, and as a thick film that acts as a resistance is formed on the surface of each electrode, the electrochemical reaction rate of the battery is reduced.
  • an acidic material eg, HF, etc.
  • the electrolyte according to the embodiment of the present invention can be efficiently applied to an overlithium positive electrode active material and a silicon-based negative electrode active material.
  • the anode active material layer may further include a binder and/or a conductive material.
  • the roles and representative examples described in the positive electrode active material for the negative electrode active material are similarly applied, and there is no particular limitation as long as the binder and the conductive material can be used in the related field.
  • the average charging voltage of the lithium secondary battery may be 4.5 V or more. This is a high-range voltage that can be expressed when the positive electrode containing the overlithium positive electrode active material and the negative electrode containing the silicon-based negative electrode active material are applied, and can be stably maintained by the functional additive included in the electrolyte solution of the present invention. have.
  • reaction solvent is concentrated, purified water (100 mL) is added to the reaction mixture, extracted with dichloromethane (100 mL), and the organic layer is washed with Brine (100 mL). The organic layer was dried over anhydrous Na 2 SO 4 , the organic solvent was concentrated, and the concentrate was purified using column chromatography to obtain the white powder compound (5.8 g, 48 % yield).
  • 1,2-Bis(chlorodimethylsilyl)ethene was synthesized using the literature method (Russian journal of General Chemistry, 2012, 82(5), 944-945) and synthesized by the method of Example 1 (4-Hydroxy-1,2 -oxathiolane-2,2-dioxide 8 g, 57.9 mmol) to obtain the compound (4.9 g, 41 % yield).
  • 1,4-Phenylenebis(chlorodimethylsilane) was synthesized by the method of Example 3 (4-Hydroxy-1,2-oxathiolane-2,2-dioxide 8 g, 57.9 mmol) by purchasing a material from Combi-Block Company, and preparing the compound (6.0 g, 45% yield) was obtained.
  • 1,2-Bis(chlorodiethylsilyl)ethene was synthesized using the literature method (Russian journal of General Chemistry, 2008, 78(9), 1668-1674) and synthesized by the method of Example 1 (4-Hydroxy-1,2 -oxathiolane-2,2-dioxide 8 g, 57.9 mmol) to obtain the compound (5.3 g, 39 % yield).
  • 1,2-bis(chloro(methyl)(vinyl)silyl)ethane was synthesized by reacting chloromethyldivinylsilane and chloromethylvinylsilane using the literature method (Russian journal of General Chemistry, 2008, 78(9), 1668-1674) and Examples The compound (4.8 g, 38 % yield) was obtained by the synthesis (4-Hydroxy-1,2-oxathiolane-2,2-dioxide 8 g, 57.9 mmol) in the method of 1.
  • An electrolyte solution was prepared in the same manner as in Examples 1 to 7 except that the additives of Examples 1 to 7 were not added.
  • An electrolyte solution was prepared in the same manner as in Examples 1 to 7, except that an additive represented by the following Chemical Formula 4 was added instead of the additives of Examples 1 to 7.
  • An electrolyte solution was prepared in the same manner as in Examples above, except that an additive represented by the following Chemical Formula 5 was added instead of the additives of Examples 1 to 7.
  • a positive electrode was prepared using a composition for forming a positive electrode active material layer comprising 94% by weight of LiCoO 2 as a positive electrode active material, 3% by weight of PVDF (polyvinylidene fluoride) as a binder, and 3% by weight of carbon black as a conductive material.
  • an anode was prepared by including a composition for forming an anode active material layer comprising 96 wt% of graphite as an anode active material, 3 wt% of PVDF as a binder, and 1 wt% of carbon black as a conductive material.
  • the electrolyte solution according to the Examples and Comparative Examples was injected, respectively, and vacuum packaging was performed to prepare a lithium secondary battery.
  • the battery prepared in Preparation Example was charged at 1C to 4.5V at room temperature (25°C), discharged at 2.75V at 1C, charged at 0.5C to 4.2V, left at high temperature (45°C) for 1 week, and then charged at 1C to 4.2V, 2.75 After 2 cycles of V 1C discharge, the capacity discharged in the 2nd cycle was measured and compared.
  • the battery prepared in Preparation Example was charged at 1C to 4.5V at a high temperature (45°C), then discharged at 2C to 2.75V to measure the initial capacity, and the capacity after repeating this 500 times was measured.
  • life retention (capacity / initial capacity after 500 repetitions) * 100, life retention at room temperature was calculated and shown in Table 2 below.

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Abstract

Selon l'un des modes de réalisation, l'invention concerne un additif pour électrolyte destiné à une batterie rechargeable, et comprenant un composé représenté par la formule chimique 1 suivante : (dans la formule chimique 1, R1, R2, R3, et R4 sont identiques ou différents l'un de l'autre, et représentent chacun indépendamment de l'hydrogène, un groupe alkyle en C1-C6 substitué ou non substitué, un groupe alcényle en C1-C6, un groupe alcynyle en C1-C6, ou un groupe aryle en C6-C10, et R5 représente un groupe alkyle en C1-C6 substitué ou non substitué, un groupe alcényle en C1-C6, un groupe alcynyle en C1-C6, ou groupe aryle en C6-C10.).
PCT/KR2021/008573 2020-07-06 2021-07-06 Additif pour électrolyte destiné à une batterie rechargeable au lithium et batterie rechargeable au lithium le comprenant WO2022010227A1 (fr)

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