WO2017164625A2 - Additif d'électrolyte non aqueux, électrolyte non aqueux contenant celui-ci pour batterie secondaire au lithium, et batterie secondaire au lithium - Google Patents

Additif d'électrolyte non aqueux, électrolyte non aqueux contenant celui-ci pour batterie secondaire au lithium, et batterie secondaire au lithium Download PDF

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WO2017164625A2
WO2017164625A2 PCT/KR2017/003032 KR2017003032W WO2017164625A2 WO 2017164625 A2 WO2017164625 A2 WO 2017164625A2 KR 2017003032 W KR2017003032 W KR 2017003032W WO 2017164625 A2 WO2017164625 A2 WO 2017164625A2
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formula
group
carbon atoms
aqueous electrolyte
substituted
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PCT/KR2017/003032
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English (en)
Korean (ko)
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WO2017164625A3 (fr
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유성훈
이경미
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주식회사 엘지화학
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Priority claimed from KR1020170034826A external-priority patent/KR102000100B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201780002362.6A priority Critical patent/CN108886166B/zh
Priority to US15/737,503 priority patent/US10601069B2/en
Priority to EP17770595.1A priority patent/EP3300157B1/fr
Priority to PL17770595T priority patent/PL3300157T3/pl
Publication of WO2017164625A2 publication Critical patent/WO2017164625A2/fr
Publication of WO2017164625A3 publication Critical patent/WO2017164625A3/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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M10/056—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
    • 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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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 a non-aqueous electrolyte additive, a non-aqueous electrolyte and a lithium secondary battery for a lithium secondary battery comprising the same, a non-aqueous electrolyte additive that can improve the capacity characteristics and cycle life characteristics at high temperature storage, a non-aqueous electrolyte for lithium secondary batteries comprising the same and It relates to a lithium secondary battery.
  • Lithium batteries specifically lithium ion batteries (LIBs) are batteries that can best meet these needs, and have been adopted as power sources for many portable devices due to their high energy density and easy design.
  • LIBs lithium ion batteries
  • lithium secondary batteries are required to maintain excellent performance not only at room temperature but also in more severe external environments such as high or low temperature environments. have.
  • the lithium ion secondary battery is composed of a carbon material negative electrode capable of storing and releasing lithium ions, a positive electrode made of a lithium-containing transition metal oxide and a non-aqueous electrolyte, and lithium ions derived from the positive electrode active material by the first charge are negative electrode active materials, such as Charge and discharge are possible because it plays a role of transferring energy while reciprocating both electrodes such as being inserted into the carbon particles and detached again during discharge.
  • the cathode active material is structurally collapsed, resulting in a decrease in the performance of the anode.
  • metal ions eluted from the surface of the anode deteriorate the cathode while electro-deposition to the cathode. Such deterioration of battery performance tends to be accelerated when the potential of the positive electrode is increased or when the battery is exposed to high temperature.
  • a first object of the present invention is to provide a nonaqueous electrolyte additive excellent in the adsorption effect on the metal ions eluted from the anode.
  • Another object of the present invention is to provide a nonaqueous electrolyte solution for a lithium secondary battery including the nonaqueous electrolyte additive.
  • Another object of the present invention is to provide a lithium secondary battery having improved overall performance by including the nonaqueous electrolyte for lithium secondary batteries.
  • non-aqueous electrolyte additive comprising at least one compound selected from the group consisting of compounds represented by formulas (I) and (II):
  • R 1 is a linear or nonlinear alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with at least one nitrile group, or an aromatic group having 6 to 8 carbon atoms unsubstituted or substituted with at least one nitrile group,
  • R 2 is a linear or nonlinear alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with at least one nitrile group, an aromatic group having 6 to 8 carbon atoms unsubstituted or substituted with at least one nitrile group, or substituted or unsubstituted with at least one nitrile group
  • R 4 is an alkylene group having 1 to 3 carbon atoms or -R 10 -C (O)-, R 10 is an alkylene group having 1 to 3 carbon atoms,
  • n and m are each independently an integer of 0 or 1.
  • R 5 is a linear or nonlinear alkyl group having 1 to 5 carbon atoms unsubstituted or substituted with hydrogen or at least one nitrile group,
  • R 6 to R 8 are each independently a linear or nonlinear alkylene group having 1 to 5 carbon atoms.
  • Ionizable lithium salts Organic solvents; And it provides a non-aqueous electrolyte for lithium secondary battery comprising the non-aqueous electrolyte additive of the present invention.
  • the nonaqueous electrolyte additive may be included in an amount of 0.5 wt% to 5 wt%, specifically 1 wt% to 5 wt%, based on the total amount of the nonaqueous electrolyte.
  • a negative electrode a positive electrode, a separator interposed between the negative electrode and the positive electrode, and a lithium secondary battery having a nonaqueous electrolyte of the present invention.
  • the metal ions eluted from the anode during charge and discharge and a non-aqueous electrolyte additive capable of forming a complex with the metal foreign matters mixed in the manufacturing process, thereby preventing the metal ions from being deposited on the surface of the cathode It is possible to produce a nonaqueous electrolytic solution which can suppress and form a more stable ionic conductive film on the cathode and anode surfaces. Furthermore, by including the nonaqueous electrolyte, a lithium secondary battery having improved overall performance such as capacity characteristics and cycle life characteristics at high temperature storage may be manufactured.
  • lithium secondary battery forms a passivation film by electrochemical oxidative decomposition reaction of electrolyte at the surface of the battery's positive electrode, especially in the presence of surface bond or activation position. Increase impedance to co-intercalation.
  • lithium ions are excessively released from the positive electrode during overcharging or high temperature storage, structural disintegration of the positive electrode active material or a chemical dissolution reaction occurs by the electrolyte solution, and ions such as Co, Mn, and Ni are eluted from the positive electrode active material. These reactions lead to deterioration of the performance of the positive electrode itself, and also cause side reactions of the electrolyte as well as collapse of the negative electrode structure, thereby degrading overall performance of the secondary battery.
  • the present invention by including at least one nitrile group and propargyl group having a metal ion adsorption performance in the structure, to provide a non-aqueous electrolyte additive that can suppress the generation of metal ions in the battery.
  • the present invention provides a nonaqueous electrolyte solution for a lithium secondary battery in which side reactions are reduced by including the nonaqueous electrolyte additive.
  • the present invention includes a non-aqueous electrolyte solution for a lithium secondary battery, thereby providing a lithium secondary battery having improved overall performance of a battery, such as capacity characteristics and cycle life characteristics at high temperature storage.
  • non-aqueous electrolyte additive comprising at least one compound selected from the group consisting of compounds represented by the following formula (I) and formula (II).
  • R 1 is a linear or nonlinear alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with at least one nitrile group, or an aromatic group having 6 to 8 carbon atoms unsubstituted or substituted with at least one nitrile group,
  • R 2 is a linear or nonlinear alkylene group having 1 to 5 carbon atoms unsubstituted or substituted with at least one nitrile group, an aromatic group having 6 to 8 carbon atoms unsubstituted or substituted with at least one nitrile group, or substituted or unsubstituted with at least one nitrile group
  • R 4 is an alkylene group having 1 to 3 carbon atoms or -R 10 -C (O)-, R 10 is an alkylene group having 1 to 3 carbon atoms,
  • n and m are each independently an integer of 0 or 1.
  • R 5 is a linear or nonlinear alkyl group having 1 to 5 carbon atoms unsubstituted or substituted with hydrogen or at least one nitrile group,
  • R 6 to R 8 are each independently a linear or nonlinear alkylene group having 1 to 5 carbon atoms.
  • Specific examples of the compound represented by Formula I include at least one compound selected from the group consisting of compounds represented by Formulas I-1 to I-39.
  • the compound represented by Chemical Formula II may include at least one compound selected from the group consisting of compounds represented by the following Chemical Formulas II-1 to II-4.
  • the polar nitrile group (ie cyano group) having a high dipole moment contained in the compounds represented by the above formulas I or II is Co, Mn eluted from the positive electrode by the chemical dissolution reaction of the electrolyte in the charge and discharge repeating process of the battery
  • the tendency to adsorb metal ions such as, or Ni, or to adsorb metallic foreign substances mixed in raw materials or manufacturing processes is very high.
  • the nitrile group in addition to the adsorption of metal ions, the non-covalent electrons of N stabilize the anion of the salt, thereby inhibiting HF generation due to salt decomposition, and form a complex structure or ligand by forming a stronger bond with the surface of the anode, especially at high temperature, A stable ion conductive film can be formed on the surface of the anode. Therefore, not only a part of the transition metal is eluted and deposited on the cathode during high temperature storage, but also a safe film is formed on the surface of the anode to suppress various side reactions and gas generation between the electrolyte and the anode, thereby swelling the battery.
  • the ring can be prevented to further improve high temperature storage characteristics such as remaining capacity and recovery capacity during high temperature storage.
  • the triple bond propazyl group contained in the compounds represented by the formula (I) or (II) is known to have a metal ion adsorption performance, and further complexes with other metal foreign substances that do not form a complex with the nitrile group. can do. Furthermore, since the propazyl group can be reduced on the surface of the negative electrode to form a stable ion conductive film on the negative electrode surface, smooth storage and release of lithium ions from the negative electrode even during high temperature storage can improve the life characteristics of the secondary battery. have.
  • one end of the triple bond is represented by the formulas (I-24), (I-37 to I-39) in which long functional groups are symmetrically bonded to both sides of the triple bond as compared to compounds containing hydrogen or short substituents.
  • the resulting polymerized film is relatively thick and the resistance is large, so that the cycle capacity retention ratio is relatively slightly decreased, whereas the adsorption effect with the metal foreign material is better, so that the voltage after high temperature storage may be relatively high. .
  • At least one or more of the compounds represented by the formula (I) or (II) having two functional groups such as nitrile group and propazyl group is used as a non-aqueous electrolyte additive, thereby eluting from the positive electrode during charge and discharge.
  • the formation of complexes with metal ions and / or metal foreign matters incorporated in the manufacturing process can suppress the electrodeposition of metal ions on the surface of the cathode, and can form a more stable ion conductive film on the electrode surface, resulting in high temperature storage. It is possible to manufacture a secondary battery having improved performance such as time capacity characteristics and cycle life characteristics.
  • nonaqueous electrolyte for a lithium secondary battery comprising the nonaqueous electrolyte additive.
  • the nonaqueous electrolyte additive may be included in an amount of about 0.5 wt% to 5 wt%, specifically 1 wt% to 5 wt%, based on the total weight of the nonaqueous electrolyte. If the content of the additive is less than 0.5% by weight, the effect of inhibiting dissolution of the metal ions described below and the improvement of capacity characteristics at high temperature storage may be insignificant. If the content of the additive is more than 5% by weight, the side reaction of the surplus nonaqueous electrolyte additive Due to the decrease in the capacity of the battery, the increase in the viscosity of the electrolyte, thereby increasing the resistance and the decrease in the ionic conductivity may cause a decrease in overall performance of the secondary battery.
  • the lithium salt contained in the non-aqueous electrolyte of the present invention may be used without limitation those conventionally used in the lithium secondary battery electrolyte, for example, the lithium salt includes Li + as a cation, anion include F -, Cl -, Br - , I -, NO 3 -, N (CN) 2 -, BF 4 -, ClO 4 -, AlO 4 -, AlCl 4 -, PF 6 -, SbF 6 -, AsF 6 -, BF 2 C 2 O 4 -, BC 4 O 8 -, (CF 3) 2 PF 4 -, (CF 3) 3 PF 3 -, (CF 3) 4 PF 2 -, (CF 3) 5 PF -, (CF 3) 6 P -, CF 3 SO 3 -, C 4 F 9 SO 3 -, CF 3 CF 2 SO 3 -, (CF 3 SO 2) 2 N -, (F 2 SO 2) 2 N -, CF 3 CF 3
  • the said lithium salt can also be used 1 type or in mixture of 2 or more types as needed.
  • the lithium salt may be appropriately changed within a range generally available, but may be included in an electrolyte solution at a concentration of 0.8 M to 1.5 M in order to obtain an effect of forming an anti-corrosion coating on the surface of the electrode.
  • the organic solvent included in the nonaqueous electrolyte of the present invention can be used without limitation those conventionally used in the electrolyte for lithium secondary batteries, for example, ether compounds, ester compounds, amide compounds, linear carbonate compounds, or cyclic carbonate compounds Etc. can be used individually or in mixture of 2 or more types, respectively. Representatively, it may include a cyclic carbonate compound, a linear carbonate compound, or a mixture thereof.
  • carbonate compounds which are typically cyclic carbonates, linear carbonates, or mixtures thereof may be included.
  • cyclic carbonate compound include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate, vinylene carbonate and fluoroethylene carbonate (FEC) are any one selected from the group consisting of or mixtures of two or more thereof.
  • linear carbonate compound examples include dimethyl carbonate (dimethyl carbonate, DMC), diethyl carbonate (diethyl carbonate, DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methylpropyl carbonate and ethylpropyl carbonate Any one selected from, or a mixture of two or more thereof may be representatively used, but is not limited thereto.
  • ethylene carbonate and propylene carbonate which are cyclic carbonates among the carbonate-based organic solvents, are highly viscous organic solvents, and thus may be preferably used because they dissociate lithium salts in the electrolyte well.
  • an electrolyte having high electrical conductivity can be made, and thus it can be used more preferably.
  • the ether in the organic solvent may be 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. It is not limited to this.
  • esters in the organic solvent include linear esters such as methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate; And cyclic esters such as ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone, or ⁇ -caprolactone, or mixtures of two or more thereof. It may be, but is not limited thereto.
  • the nonaqueous electrolyte of the present invention may further include an additive for forming an SEI film, if necessary.
  • an additive for forming SEI film which can be used in the present invention, vinylene carbonate, vinyl ethylene carbonate, fluoroethylene carbonate, vinyl ethylene carbonate, cyclic sulfite, saturated sultone, unsaturated sultone, acyclic sulfone, etc. may be used alone or in combination. It can mix and use the above.
  • the cyclic sulfites include ethylene sulfite, methyl ethylene sulfite, ethyl ethylene sulfite, 4,5-dimethyl ethylene sulfite, 4,5-diethyl ethylene sulfite, propylene sulfite, 4,5-dimethyl Propylene sulfite, 4,5-diethyl propylene sulfite, 4,6-dimethyl propylene sulfite, 4,6-diethyl propylene sulfite, 1,3-butylene glycol sulfite, and the like. Examples thereof include 1,3-propane sultone and 1,4-butane sultone.
  • unsaturated sultone examples include ethene sultone, 1,3-propene sultone, 1,4-butene sultone, 1-methyl-1,3 -Propene sulfone, and the like, and acyclic sulfones include divinyl sulfone, dimethyl sulfone, diethyl sulfone, methylethyl sulfone, and methyl vinyl sulfone.
  • the secondary battery comprising a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode and a non-aqueous electrolyte
  • a lithium secondary battery comprising the non-aqueous electrolyte of the present invention as the non-aqueous electrolyte.
  • the lithium secondary battery of the present invention may be prepared by injecting the nonaqueous electrolyte of the present invention into an electrode structure consisting of a cathode, a cathode, and a separator interposed between the cathode and the anode.
  • the positive electrode, the negative electrode, and the separator constituting the electrode structure may be used all those conventionally used in the manufacture of a lithium secondary battery.
  • the positive electrode may be manufactured by forming a positive electrode mixture layer on the positive electrode current collector.
  • the cathode mixture layer may be formed by coating a cathode slurry including a cathode active material, a binder, a conductive material, a solvent, and the like, followed by drying and rolling.
  • the positive electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the positive electrode current collector may be formed of stainless steel, aluminum, nickel, titanium, calcined carbon, or carbon on the surface of aluminum or stainless steel. Surface treated with nickel, titanium, silver, or the like may be used.
  • the positive electrode active material is a compound capable of reversible intercalation and deintercalation of lithium, and may specifically include a lithium composite metal oxide containing lithium and one or more metals such as cobalt, manganese, nickel or aluminum. have. More specifically, the lithium composite metal oxide may be lithium-manganese oxides (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxides (eg, LiCoO 2, etc.), lithium-nickel oxides, and the like.
  • the lithium composite metal oxide may be lithium-manganese oxides (eg, LiMnO 2 , LiMn 2 O 4, etc.), lithium-cobalt oxides (eg, LiCoO 2, etc.), lithium-nickel oxides, 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.g., LiNi 1-Y1 Co Y1 O 2 (here, 0 ⁇ Y1 ⁇ 1) and the like
  • lithium-manganese-cobalt oxide e.
  • LiCoO 2 , LiMnO 2 , LiNiO 2 , and lithium nickel manganese cobalt oxides may be improved in capacity and stability of the battery.
  • the lithium composite metal oxide is Li (Ni 0.6 Mn 0.2 Co 0.2 ) O 2 in consideration of the remarkable improvement effect according to the type and content ratio control of the element forming the lithium composite metal oxide.
  • Li (Ni 0.5 Mn 0.3 Co 0.2 ) O 2 Li (Ni 0.7 Mn 0.15 Co 0.15 ) O 2, or Li (Ni 0.8 Mn 0.1 Co 0.1 ) O 2 , and the like, and any one or a mixture of two or more thereof may be used. have.
  • the cathode active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the cathode slurry.
  • the conductive material is typically added at 1 to 30% by weight based on the total weight of the positive electrode slurry.
  • Such a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite; Carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys 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.
  • Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack, and EC, which are acetylene black series. (Armak Company), Vulcan XC-72 (manufactured by Cabot Company), and Super P (manufactured by Timcal).
  • the binder is a component that assists in bonding the active material and the conductive material and bonding to the current collector, and is generally added in an amount of 1 to 30 wt% based on the total weight of the positive electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • the solvent may include an organic solvent such as N-methyl-2-pyrrolidone (NMP), and may be used in an amount that becomes a desirable viscosity when including the positive electrode active material and optionally a binder and a conductive material.
  • NMP N-methyl-2-pyrrolidone
  • the concentration of the solids in the positive electrode active material and, optionally, the slurry including the binder and the conductive material may be 50 wt% to 95 wt%, preferably 70 wt% to 90 wt%.
  • the negative electrode may be prepared by forming a negative electrode mixture layer on the negative electrode current collector.
  • the negative electrode mixture layer may be formed by coating a slurry including a negative electrode active material, a binder, a conductive material, a solvent, and the like, followed by drying and rolling.
  • the negative electrode current collector generally has a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery.
  • copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like on the surface, aluminum-cadmium alloy and the like can be used.
  • fine concavities and convexities may be formed on the surface to enhance the bonding strength of the negative electrode active material, and may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the negative electrode active material natural graphite, artificial graphite, carbonaceous material; Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; Alloys composed of the metals (Me); Oxides of the above metals; And one or two or more negative electrode active materials selected from the group consisting of the above metals and a composite of carbon.
  • Metals (Me) that are lithium-containing titanium composite oxide (LTO), Si, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe
  • Alloys composed of the metals (Me) Oxides of the above metals
  • one or two or more negative electrode active materials selected from the group consisting of the above metals and a composite of carbon.
  • the negative active material may be included in an amount of 80 wt% to 99 wt% based on the total weight of the negative electrode slurry.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 30 wt% based on the total weight of the negative electrode slurry.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluor Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • the conductive material is a component for further improving the conductivity of the negative electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of the negative electrode slurry.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys 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 solvent may include an organic solvent such as water or NMP, alcohol, etc., and may be used in an amount that becomes a desirable viscosity when including the negative electrode active material and optionally a binder and a conductive material.
  • concentration of the solids in the slurry including the negative electrode active material, and optionally the binder and the conductive material may be 50% to 95% by weight, preferably 70% to 90% by weight.
  • porous polymer films conventionally used as separators for example, polyolefins such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer, etc.
  • the porous polymer film made of the polymer may be used alone or by laminating them, or a conventional porous nonwoven fabric, for example, a non-woven fabric made of high melting point glass fiber, polyethylene terephthalate fiber, or the like may be used. It is not.
  • the external shape of the lithium secondary battery of the present invention is not particularly limited, but may be cylindrical, square, pouch type, or coin type using a can.
  • a positive active material slurry was prepared by adding pyrrolidone (NMP) in a ratio of 100: 40 parts by weight.
  • 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 prepare a positive electrode.
  • Natural graphite as a negative electrode active material PVDF as a binder and carbon black as a conductive material were added to NMP as a solvent at a ratio of 100: 100 parts by weight to prepare a negative electrode active material slurry.
  • the negative electrode active material slurry was applied to a negative electrode current collector (Cu thin film) having a thickness of 90 ⁇ m, dried, and roll pressed to prepare a negative electrode.
  • the positive electrode and the negative electrode prepared by the above-described method were laminated together with a polyethylene porous film to prepare an electrode assembly. Then, the prepared nonaqueous electrolyte was poured into the battery case, and the lithium secondary battery was prepared by sealing.
  • Example 1 In the preparation of the non-aqueous electrolyte of Example 1, except that each of the additives in the amount shown in Table 1, the same method as in Example 1 to the non-aqueous electrolyte of Examples 2 to 28 and a secondary battery comprising the same Were prepared respectively.
  • a positive active material slurry was prepared by adding pyrrolidone (NMP) in a ratio of 100: 40 parts by weight.
  • 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 prepare a positive electrode.
  • the prepared positive electrode was punched out for a coin-type battery, and then fixed with three Fe powders having an average particle diameter (D50) of about 200 ⁇ m on the surface of the positive electrode, and then the non-aqueous electrolyte was injected to prepare a coin-type half battery.
  • D50 average particle diameter
  • Example 29 In the preparation of the non-aqueous electrolyte of Example 29, except that each of the additives in the amounts shown in Table 2, the same method as in Example 29, the non-aqueous electrolyte of Examples 30 to 56 and a secondary battery comprising the same Were prepared respectively.
  • a nonaqueous electrolyte and a secondary battery including the same were prepared in the same manner as in Example 1, except that no additive was included in the preparation of the nonaqueous electrolyte of Example 1.
  • the non-aqueous electrolyte was prepared in the same manner as in Example 1, except that 0.3 g of the compound of Formula a was included instead of the compound of Formula I-1 when preparing the non-aqueous electrolyte of Example 1. And a secondary battery comprising the same was prepared.
  • a nonaqueous electrolyte and a coin-type half-cell including the same were prepared in the same manner as in Example 29, except that no additive was included in the preparation of the nonaqueous electrolyte of Example 29.
  • Each of the secondary batteries prepared in Examples 1 to 28 and Comparative Examples 1 to 9 was subjected to constant current / constant voltage condition charging and 0.05C cut off charging to 4.35V at 0.8C rate, and discharged to 0.5C 3.0V (initial) Discharge capacity). Then, constant current / constant voltage condition charging and 0.05C cut off charging were performed up to 4.35V at 0.8C rate and stored at 60 ° C. for 2 weeks. Thereafter, the battery was discharged at 0.5C 3.0V at room temperature, and the discharge amount thereof was measured (remaining discharge amount). The discharge amount was measured again by charging the constant current / constant voltage condition up to 0.8C rate, 4.35V, 0.05C cut off charging, and 0.5C 3.0V (recovery discharge amount).
  • the remaining discharge amount and the recovery discharge amount are expressed in% relative to the initial discharge amount, and are shown in Table 1 below.
  • Each of the secondary batteries prepared in Examples 1 to 28 and Comparative Examples 1 to 9 was subjected to constant current / constant voltage condition charging and 0.05C cut off charging to 0.85C at 4.35V, and discharged at 0.5C to 3.0V. Then, the cycle capacity retention after 200 cycles was performed by performing constant current / constant voltage condition charging and 0.05C cut-off charging up to 4.35V at 0.8C rate, and discharging at 0.5C 3.0V at room temperature as one cycle. It is shown in Table 1, expressed as a percentage of one cycle capacity.
  • the amount of residual discharge at high temperature storage was about It can be seen that the recovery discharge amount is 80% or more, about 92% or more, and the cycle capacity retention rate is about 87% or more.
  • the secondary battery of Comparative Example 1 which does not use an additive, has a residual discharge amount of about 64%, a recovery discharge amount of about 80%, and a cycle capacity retention rate of about 60% at high temperature storage. It can be seen that the degradation compared to the secondary battery of 28 to.
  • the residual discharge amount at the high temperature storage of the secondary batteries of Comparative Examples 2 to 9 including the compound of Formulas a to d as an additive as a non-aqueous electrolyte additive is 80% or less, recovery discharge amount is 87% or less, and the capacity retention ratio is 70 It can be confirmed that all of the secondary batteries of Examples 1 to 28 are lowered to less than or equal to%.
  • Each coin-type secondary battery manufactured in Examples 29 to 56 and Comparative Examples 10 to 18 was subjected to constant current / constant voltage condition charging and 0.05C cut off charging to 4.35V at 0.8C rate, and discharged to 0.5C 3.0V. It was.
  • Each battery is made of five batteries, and the number of batteries capable of charging and discharging is shown in Table 2 below.
  • the battery capable of charging and discharging was charged under constant current / constant voltage conditions up to 4.35 V at 0.8 C rate and stored at 45 ° C. for 6 days.
  • the voltage at 45 ° C. after storage was measured and the results are shown in Table 2 below.
  • the secondary batteries of Examples 29 to 56 since the compounds containing the nitrile group and the propazyl group included as additives form a complex with Fe foreign material to suppress metal elution, most of the batteries It can be seen that charging and discharging are possible and the voltage is maintained at about 4.01V or higher even after high temperature storage.
  • the secondary batteries of Comparative Examples 11, 12, 14, 15, 16, and 18 including the compounds of Formulas (a) to (d) as non-aqueous electrolyte additives were able to be charged and discharged in some cells, but the voltage was weak after high temperature storage. It can be seen that the drop below 3.7V.

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Abstract

La présente invention concerne un additif d'électrolyte non aqueux, un électrolyte non aqueux contenant celui-ci pour une batterie secondaire au lithium, et une batterie secondaire au lithium. Spécifiquement, la présente invention concerne un additif d'électrolyte non aqueux ayant un groupe nitrile et un groupe propargyle, un électrolyte non aqueux pour une batterie secondaire au lithium, l'électrolyte non aqueux pouvant améliorer les caractéristiques de capacité et les caractéristiques de durée de vie à température élevée en contenant l'additif d'électrolyte non aqueux, et une batterie secondaire au lithium.
PCT/KR2017/003032 2016-03-23 2017-03-21 Additif d'électrolyte non aqueux, électrolyte non aqueux contenant celui-ci pour batterie secondaire au lithium, et batterie secondaire au lithium WO2017164625A2 (fr)

Priority Applications (4)

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CN201780002362.6A CN108886166B (zh) 2016-03-23 2017-03-21 非水电解质添加剂、和包含该非水电解质添加剂的锂二次电池用非水电解质以及锂二次电池
US15/737,503 US10601069B2 (en) 2016-03-23 2017-03-21 Non-aqueous electrolyte additive, and non-aqueous electrolyte for lithium secondary battery comprising the same and lithium secondary battery
EP17770595.1A EP3300157B1 (fr) 2016-03-23 2017-03-21 Additif d'électrolyte non aqueux, électrolyte non aqueux contenant celui-ci pour batterie secondaire au lithium, et batterie secondaire au lithium
PL17770595T PL3300157T3 (pl) 2016-03-23 2017-03-21 Dodatek do niewodnego elektrolitu, niewodny elektrolit go zawierający dla akumulatora litowego i akumulator litowy

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KR1020170034826A KR102000100B1 (ko) 2016-03-23 2017-03-20 비수전해액 첨가제, 이를 포함하는 리튬 이차전지용 비수전해액 및 리튬 이차전지

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