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WO2018048188A1 - Additif d'électrolyte et batterie secondaire au lithium le comprenant - Google Patents

Additif d'électrolyte et batterie secondaire au lithium le comprenant Download PDF

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Publication number
WO2018048188A1
WO2018048188A1 PCT/KR2017/009758 KR2017009758W WO2018048188A1 WO 2018048188 A1 WO2018048188 A1 WO 2018048188A1 KR 2017009758 W KR2017009758 W KR 2017009758W WO 2018048188 A1 WO2018048188 A1 WO 2018048188A1
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Prior art keywords
anion
additive
electrolyte solution
group
lithium
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PCT/KR2017/009758
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English (en)
Korean (ko)
Inventor
김재윤
임형규
이종현
한지성
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Soulbrain Co Ltd
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Soulbrain Co Ltd
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Priority claimed from KR1020160174854A external-priority patent/KR20180027987A/ko
Priority claimed from KR1020170081412A external-priority patent/KR101980315B1/ko
Application filed by Soulbrain Co Ltd filed Critical Soulbrain Co Ltd
Priority to CN201780055004.1A priority Critical patent/CN109690864A/zh
Priority to JP2019513038A priority patent/JP2019526914A/ja
Priority to EP17849072.8A priority patent/EP3512024A4/fr
Publication of WO2018048188A1 publication Critical patent/WO2018048188A1/fr
Priority to US16/293,685 priority patent/US11024881B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • H01M10/0569—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 an electrolyte additive and a lithium secondary battery including the same in a nonaqueous electrolyte.
  • Lithium secondary batteries are the batteries that can best meet these demands, and research on these is being actively conducted.
  • a lithium secondary battery is a battery composed of a positive electrode, a negative electrode, and an electrolyte solution and a separator that provides a movement path of lithium ions between the positive electrode and the negative electrode, and is used for oxidation and reduction reactions when lithium ions are occluded and discharged from the positive electrode and the negative electrode. Thereby generating electrical energy.
  • the average discharge voltage of the lithium secondary battery is about 3.6 to 3.7 V, which is one of the advantages of higher discharge voltage than other alkaline batteries, nickel-cadmium batteries, and the like.
  • an electrochemically stable electrolyte composition is required in the charge and discharge voltage range of 0 to 4.2V.
  • lithium ions derived from the positive electrode active material such as lithium metal oxide are moved to the negative electrode active material such as graphite and inserted into the interlayer of the negative electrode active material.
  • the electrolyte and the carbon constituting the negative electrode active material react on the surface of the negative electrode active material such as graphite to generate a compound such as Li 2 CO 3 , Li 2 O, or LiOH.
  • SEI Solid Electrolyte Interface
  • the SEI membrane acts as an ion tunnel, passing only lithium ions.
  • the SEI membrane is an effect of this ion tunnel, which prevents the breakdown of the negative electrode structure by intercalation of organic solvent molecules having a large molecular weight moving with lithium ions in the electrolyte between the layers of the negative electrode active material. Therefore, by preventing contact between the electrolyte solution and the negative electrode active material, decomposition of the electrolyte solution does not occur, and the amount of lithium ions in the electrolyte solution is reversibly maintained to maintain stable charge and discharge.
  • the problem to be solved of the present invention is to provide a novel electrolyte additive.
  • a lithium secondary battery comprising a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a separator interposed between the positive electrode and the negative electrode and a non-aqueous electrolyte containing the electrolyte additive of the present invention To provide.
  • the present invention provides an electrolyte additive comprising a salt of a nitrogen atom-containing compound-derived anion and Cs + or Rb + .
  • the present invention provides an electrolyte additive which further comprises lithium difluoro bisoxalato phosphate in the electrolyte additive.
  • the present invention provides a non-aqueous electrolyte comprising a lithium salt, a non-aqueous organic solvent and the electrolyte additive.
  • the present invention also provides a lithium secondary battery including a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a separator interposed between the positive electrode and the negative electrode and the non-aqueous electrolyte.
  • the secondary battery formed by including the electrolyte additive according to an embodiment of the present invention is excellent in high temperature and low temperature life characteristics, high temperature storage characteristics and thickness change rate.
  • a secondary battery formed by including a compound containing a salt of a nitrogen atom-containing compound-derived anion and Cs + or Rb + and an electrolyte additive comprising lithium difluoro bisoxalato phosphate according to another embodiment of the present invention Excellent high temperature output characteristics.
  • the novel electrolyte additive according to one embodiment of the present invention may include a salt of a nitrogen atom-containing compound-derived anion and Cs + or Rb + .
  • the nitrogen atom-containing compound-derived anion may include one or more selected from the group consisting of an amide anion, an imide anion, a nitrile anion, a nitrite anion, and a nitrate anion.
  • the amide-based anion is one selected from the group consisting of dimethylformamide anion, dimethylacetamide anion, diethylformamide anion, diethylacetamide anion, methylethylformamide anion, and methylethylacetamide anion. It may be included above.
  • imide-based anion may be represented by Formula 1 below.
  • R 1 and R 2 are each a fluoro group or a fluoroalkyl group having 1 to 4 carbon atoms, or R 1 and R 2 are connected to each other to form a fluoro cycloalkylene ring having 1 to 4 carbon atoms You may also do it.
  • the nitrile anions include acetonitrile anion, propionitrile anion, butyronitrile anion, valeronitrile anion, caprylonitrile anion, heptanenitrile anion, cyclopentane carbonitrile anion, cyclohexane carbonitrile anion, and 2-fluorobenzo Nitrile anion, 4-fluorobenzonitrile anion, difluorobenzonitrile anion, trifluorobenzonitrile anion, phenylacetonitrile anion, 2-fluorophenylacetonitrile anion, and 4-fluorophenylacetonitrile anion It may be one containing at least one selected from the group.
  • the compound represented by Chemical Formula 1 may include one or more selected from the group consisting of the following Chemical Formulas 2 to 6.
  • the electrolyte additive is cesium bis (trifluoromethanesulfonyl) imide, cesium nitrate, rubidium bis (trifluoromethanesulfonyl) imide, rubidium nitrate and cesium bis ( It may be one containing one or more selected from the group consisting of fluorosulfonyl) imide.
  • the present invention can provide a non-aqueous electrolyte solution containing a lithium salt, a non-aqueous organic solvent and the electrolyte additive.
  • the additive may form a film on the surface of the positive electrode and the negative electrode in the electrolyte.
  • an oxidation reaction is performed on the surface of the cathode and a reduction reaction is performed on the surface of the anode.
  • the additive according to an embodiment of the present invention may form a film on the surfaces of the cathode and the anode to effectively control the dissolution of lithium ions generated from the anode, and may prevent a phenomenon in which the anode is decomposed.
  • the film formed by the additive on the surface of the cathode is partially decomposed through the reduction reaction during charging and discharging, but the decomposed additive may move back to the surface of the anode and form a film on the surface of the anode again through an oxidation reaction. have. Therefore, even after repeated charging and discharging several times, the additive can maintain the film on the surface of the positive electrode, thereby effectively preventing excessive elution of lithium ions at the positive electrode.
  • Cs + or Rb + of the additive according to an embodiment of the present invention is an ion of an alkali element, which is due to the chemical properties of Li + present in the positive electrode and the negative electrode. It is assumed. Therefore, the secondary battery according to an embodiment of the present invention does not collapse the structure even if the positive electrode is repeatedly charged and discharged, it can be effectively maintained to improve the high temperature and low temperature life characteristics of the secondary battery.
  • the additive according to the embodiment of the present invention may improve the safety of the battery by reducing side reactions and generated contact surfaces between the positive electrode and the electrolyte. Due to the characteristics of the high reaction potential and little change in the reaction potential with the progress of the cycle, it is possible to prevent the degradation of the battery due to the conventional additive decomposition and sudden change of the reaction potential. Furthermore, the additive forms a stable film through an oxidation reaction at the anode, thereby preventing decomposition of the anode and suppressing elution, thereby more stably protecting the anode under a high voltage environment.
  • the additive may further include a heterogeneous additive to improve the stability of the lithium secondary battery or the output.
  • This may further include lithium difluoro bisoxalato phosphate in an additive comprising a salt of the above-described nitrogen atom-containing compound anion and Cs + or Rb + , more specifically cesium bis (trifluoromethane One or more selected from the group consisting of sulfonyl) imide, cesium nitrate, rubidium bis (trifluoromethanesulfonyl) imide rubidium nitrate and cesium bis (fluorosulfonyl) imide and lithium difluoro bis It may be one containing oxalato phosphate.
  • Lithium difluoro bisoxalato phosphate can form a stable SEI film on the surface of the anode and cathode.
  • An additive comprising a salt of a nitrogen atom-containing compound anion and Cs + or Rb + is lithium difluoro bisoxalato phosphate.
  • the SEI film of the negative electrode and the positive electrode formed from lithium difluoro bisoxalato phosphate can be formed more uniformly, and the movement of lithium ions becomes easier according to the formation of the uniform film. Better output characteristics can be obtained.
  • the additive including the salt with Cs + or Rb + and lithium difluoro bisoxalato phosphate are preferably included in the electrolyte at a weight ratio of 1: 1 to 1: 4.
  • the content of the additive may be 0.05 to 10% by weight based on the total amount of the non-aqueous electrolyte.
  • the content of the additive may be 0.1 to 3% by weight based on the total amount of the non-aqueous electrolyte.
  • the content of the additive is less than 0.05% by weight, the effect of improving the low temperature and high temperature storage characteristics and the high temperature life characteristics of the lithium secondary battery is insignificant, and if the content of the additive exceeds 10% by weight due to excessive film formation, resistance This increasing problem can occur.
  • the lithium salt may be used a lithium salt commonly used in the art, for example LiPF 6 , LiFSI, LiAsF 6 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiBF 4 , LiSbF 6 , LiN It may include one or more selected from the group consisting of (C 2 F 5 SO 2 ) 2 , LiAlO 4 , LiAlCl 4 , LiSO 3 CF 3 , LiTFSI, LiDFOB, and LiClO 4 .
  • the lithium salt preferably has a concentration in the non-aqueous electrolyte solution of 0.01 mole / l to 2 mole / l, more preferably 0.01 mole / l to 1 mole / l.
  • organic solvents commonly used in lithium secondary battery electrolytes can be used without limitation, for example, ethers, esters, amides, linear carbonates, cyclic carbonates, phosphoric acid compounds, A nitrile compound, a fluorinated ether compound, a fluorinated aromatic compound, etc. can be used individually or in mixture of 2 or more types, respectively.
  • 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 It may include one or more selected from the group consisting of carbonates, vinylene carbonates, and halides thereof.
  • linear carbonate compounds include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC) and ethylpropyl carbonate (EPC). It may include one or more selected from the group consisting of, but is not limited thereto.
  • the cyclic carbonate in the carbonate-based electrolyte solvent preferably includes propylene carbonate, ethylene carbonate, and mixtures thereof, and may be preferably used because it dissociates lithium salt in the electrolyte well because of high dielectric constant as a high-viscosity organic solvent.
  • diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, and a linear carbonene, which is a mixture thereof, with the cyclic carbonate can be more preferably used because low viscosity, low dielectric constant linear carbonate can be mixed in an appropriate ratio to make an electrolyte having high electrical conductivity.
  • ester in the electrolyte solvent is methyl acetate, ethyl acetate, propyl acetate, ethyl propionate (EP), propyl propionate, methyl propionate (MP), ⁇ -butyrolactone, ⁇ -valerolactone , ⁇ -caprolactone, ⁇ -valerolactone and ⁇ -caprolactone, and may include one or more selected from among them, particularly low viscosity ethyl propionate (EP), propyl propionate, It is preferred to include methyl propionate (MP) and mixtures thereof.
  • the phosphoric acid solvent and the mononitrile solvent may be substituted with a fluorine atom (F).
  • F fluorine atom
  • the solvent is substituted with a halogen element, the flame retardancy is further increased, but when the solvent is substituted with Cl, Br, or I, the reactivity of the solvent increases together, which is not preferable as an electrolyte solution.
  • non-limiting examples of the phosphate compound include trimethylphosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, triphenylphosphine oxide, diethyl methylphosphonate, di Methyl methylphosphonate, diphenyl methylphosphonate, bis (2,2,2-trifluoroethyl) methylphosphonate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, ethyl methyl phenyl phosphate and the like.
  • These phosphoric acid solvents may be used alone or in combination of two or more thereof.
  • non-limiting examples of the nitrile-based compound include acetonitrile, propionitrile, butyronitrile, valeronitrile, caprylonitrile, heptanenitrile, cyclopentane carbonitrile, cyclohexane carbonitrile, 2-fluorobenzo Nitrile, 4-fluorobenzonitrile, difluorobenzonitrile, trifluorobenzonitrile, phenylacetonitrile, 2-fluorophenylacetonitrile, 4-fluorophenylacetonitrile and the like.
  • These nitrile solvents can be used individually or in mixture of 2 or more types.
  • fluorinated ether compound examples include bis-, 2,2-trifluoroethyl ether, n-butyl 1,1,2,2-tetrafluoroethyl ether, 2,2,3, 3,3-pentafluoropropyl methyl ether, 2,2,3,3,3-pentafluoropropyl 1,1,2,2-tetrafluoroethyl ether, 1,1,2,2-tetrafluoroethyl Methyl ether, 1,1,2,2-tetrafluoroethyl ethyl ether, trifluoroethyl dodecafluorohexyl ether, and the like.
  • fluorinated ether solvents may be used alone or in combination of two or more thereof.
  • Non-limiting examples of aromatic compound solvents include halogenated benzene compounds such as chlorobenzene, chlorotoluene and fluorobenzene, tert-butyl benzene, tert-pentyl benzene, cyclohexyl benzene, hydrogen biphenyl and hydrogenated terphenyl.
  • Alkylated aromatic compounds such as these, are mentioned.
  • the alkyl group of the said alkylated aromatic compound may be halogenated, and the fluorinated thing is mentioned as an example. Examples of such fluorinated compounds include trifluoro methoxy benzene and the like.
  • the lithium secondary battery according to an embodiment of the present invention may include a positive electrode including a positive electrode active material, a negative electrode including a negative electrode active material, a separator interposed between the positive electrode and the negative electrode and the non-aqueous electrolyte solution.
  • the positive electrode active material can be used without limitation as long as it is a compound capable of intercalating / deintercalating lithium.
  • the positive electrode active material is a spinel lithium transition metal oxide having a thin crystal layered rock salt structure, an olivine structure, and a cubic structure having high capacity characteristics, in addition to V 2 O 5 , TiS , MoS may include one or more selected from the group consisting of. More specifically, for example, the composition may include one or more selected from the group consisting of compounds represented by Formulas 7 to 9:
  • the positive electrode active material is preferably Li [Ni 0.6 Co 0.2 Mn 0.2 ] O 2 , Li (Ni 0.5 Co 0.2 Mn 0.3 ) O 2 , Li [Ni 1/3 Co 1/3 Mn 1/3 ] O 2 , and It may include one or more selected from the group consisting of LiCoO 2 .
  • the Li [Ni a Co b Mn c ] O 2 in the positive electrode can have a synergistic effect in combination with the compound of formula (1) of the present invention.
  • the positive electrode active material of the lithium-nickel-manganese-cobalt-based oxide As the content of Ni in the transition metal increases, Li + 1 ions and Ni + 2 ions in the layered structure of the positive electrode active material change positions during charge and discharge. (cation mixing) may occur and the structure may become unstable, and thus the positive electrode active material may cause side reactions with the electrolyte, or dissolution of transition metals. Therefore, when using the electrolyte additive of the formula (1) according to an embodiment of the present invention, it is assumed that the phenomenon of the cation mixing (cation mixing) can be minimized.
  • the negative electrode active material includes amorphous carbon or crystalline carbon, specifically, carbon such as non-graphitized carbon, graphite carbon; LixFe 2 O 3 (0 ⁇ x ⁇ 1), LixWO 2 (0 ⁇ x ⁇ 1 ), SnxMe 1 - x Me ' y O z (Me: Mn, Fe, Pb, Ge; Me': Al, B, P , Metal complex oxides such as Si, Group 1, 2, 3 Group elements of the periodic table, halogen, 0 ⁇ x ⁇ 1, 1 ⁇ y ⁇ 3, 1 ⁇ z ⁇ 8); Lithium metal; Lithium alloys; Silicon-based alloys; Tin-based alloys; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 ,
  • the separator is a porous polymer film, for example, a porous polymer film made of a polyolefin-based polymer such as ethylene homopolymer, propylene homopolymer, ethylene / butene copolymer, ethylene / hexene copolymer and ethylene / methacrylate copolymer This may be a single or two or more laminated.
  • a porous nonwoven fabrics such as high-melting glass fibers, polyethylene terephthalate fibers, and the like may be used, but are not limited thereto.
  • the positive electrode and / or the negative electrode may be prepared by mixing and stirring a binder, a solvent, a conductive agent and a dispersant which may be commonly used as needed, to prepare a slurry, and then applying the same to a current collector and compressing the same.
  • the binder may be polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HEP), polyvinylidene fluoride (polyvinylidenefluoride), polyacrylonitrile, polymethylmethacrylate, Polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), Various kinds of binder polymers such as sulfonated EPDM, styrene butyrene rubber (SBR), fluorine rubber, various copolymers and the like may be used.
  • PVDF-co-HEP polyvinylidene fluoride-hexafluoropropylene copolymer
  • SBR styrene butyrene rubber
  • the lithium secondary battery including the additive may undergo a formation and aging process to secure the performance of the secondary battery.
  • the formation process is to activate the battery by repeatedly charging and discharging the battery after assembling the battery. Lithium ions from the lithium metal oxide used as the anode during charging are moved to the carbon electrode used as the cathode, where lithium Due to its high reactivity, it reacts with the carbon anode to form compounds such as Li 2 CO 3 , LiO, LiOH, and these form a solid electrolyte interface (SEI) film on the surface of the cathode.
  • SEI solid electrolyte interface
  • the aging process is to stabilize the battery activated as described above for a certain period of time.
  • the SEI film is formed on the surface of the cathode through the formation process, and the SEI film is generally stabilized by standing at room temperature for a certain period of time, that is, at room temperature.
  • Lithium secondary battery using a non-aqueous liquid containing an additive according to an embodiment of the present invention not only at room temperature aging process, but also at a high temperature aging process by the Cs, Rb which is the cognate element of lithium, It can be seen that there is no problem such as reduced stability or decomposition thereof.
  • the formation step is not particularly limited and may be half charged at 1.0 to 3.8V or full charge at 3.8 to 4.3V.
  • the C-RATE may be charged for 5 minutes to 1 hour at a current density of 0.1C ⁇ 2C.
  • the aging step may be carried out at room temperature or in a temperature range (high temperature) of 60 to 100 °C. If the temperature exceeds 100 ° C., there is a possibility that the packaging material may rupture or the battery may ignite due to evaporation of the electrolyte.
  • the remaining capacity SOC of the battery may be in any range from 100% when the battery is fully charged to 0% due to discharge.
  • the storage time is not particularly limited, but is preferably about 1 hour to 1 week.
  • the external shape of the lithium secondary battery according to an embodiment of the present invention is not particularly limited, but may be cylindrical, rectangular, pouch type, or coin type using a can.
  • Ethylene carbonate (EC): ethylmethyl carbonate (EMC): diethyl carbonate (DEC) 30:50:20 (volume ratio)
  • EMC ethylmethyl carbonate
  • DEC diethyl carbonate
  • NMP solvent N-methyl-2-pyrrolidone
  • the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
  • a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive agent at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
  • the negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
  • Cu copper
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 0.7 wt% of cesium bis (trifluoromethanesulfonyl) imide was added as the additive to 0.7 wt% based on the total amount of the non-aqueous electrolyte. It was.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 1 wt% of cesium bis (trifluoromethanesulfonyl) imide was added as the additive based on the total amount of the nonaqueous electrolyte. It was.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 3 wt% of cesium bis (trifluoromethanesulfonyl) imide was added as the additive based on the total amount of the non-aqueous electrolyte solution. It was.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that cesium nitrate was used in an amount of 0.5% by weight instead of cesium bis (trifluoromethanesulfonyl) imide.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 0.7 wt% of cesium nitrate was used instead of cesium bis (trifluoromethanesulfonyl) imide as the additive.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 1.0 wt% of cesium nitrate was used instead of the cesium bis (trifluoromethanesulfonyl) imide.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 3.0 wt% of cesium nitrate was used instead of the cesium bis (trifluoromethanesulfonyl) imide.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 0.5 wt% of rubidium bis (trifluoromethanesulfonyl) imide was used instead of cesium bis (trifluoromethanesulfonyl) imide as the additive.
  • the battery was prepared.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 0.5 wt% of rubidium nitrate was used instead of cesium bis (trifluoromethanesulfonyl) imide as the additive.
  • Cesium nitrate instead of cesium bis (trifluoromethanesulfonyl) imide as the additive was added 0.5% by weight based on the total amount of the non-aqueous electrolyte and 0.5% by weight of the lithium difluoro bisoxalatophosphate.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except for the above.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that the cathode active material was used as Li [Ni 1/3 Co 1/3 Mn 1/3 ] O 2 .
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that the positive electrode active material was used as LiCoO 2 .
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that cesium bis (trifluoromethanesulfonyl) imide additive was added at 0.03% by weight in the nonaqueous electrolyte solution.
  • Cesium bis (trifluoromethanesulfonyl) imide in the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that the additive was added in an amount of 11 wt%.
  • Cesium nitrate instead of cesium bis (trifluoromethanesulfonyl) imide in the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that the additive was added at 0.03% by weight.
  • Cesium nitrate instead of cesium bis (trifluoromethanesulfonyl) imide in the non-aqueous electrolyte A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that the additive was added in an amount of 11 wt%.
  • the lithium secondary battery is charged at a constant current until the voltage reaches 4.20 V (vs. Li) at a high temperature (45 ° C.) at a current of 1.5 C, and then cuts off at a current of 0.05 C at a constant voltage mode while maintaining 4.20 V. (cut-off). Subsequently, discharge was performed at a constant current of 1.5 C rate (1st cycle) until the voltage reached 3.0 V (vs. Li). The same cycle was repeated up to 300 cycles.
  • the experimental results are shown in Table 1 and Table 2.
  • the lithium secondary battery was operated at room temperature (25 ° C) -low temperature (-10 ° C) -low temperature (-20 ° C) -room temperature (25 ° C) at a current of 0.5C rate until the voltage reached 4.20V (vs. Li). Constant current charge was then cut-off at a current of 0.05 C rate while maintaining 4.20 V in constant voltage mode. Subsequently, it discharged at the constant current of 0.5 C rate (1st cycle) until the voltage reached 3.0V (vs. Li) at the time of discharge. The cycle was repeated 10 times in sequence for each temperature.
  • Example 1 899.25 536.72 218.85 415.82 46.24
  • Example 2 898.16 534.12 217.5 413.17 46.00
  • Example 3 897.84 532.48 216.82 411.15 45.79
  • Example 4 896.68 529.28 214.96 405.29 45.20
  • Example 5 896.81 533.18 215.18 412.3 45.97
  • Example 6 895.18 531.84 214.79 407.17 45.48
  • Example 7 893.37 529.76 213.14 402.23 45.02
  • Example 9 890.84 527.18 208.24 405.74 45.55
  • Example 10 887.21 526.87
  • Example 1 47.5 79 166.32
  • Example 2 47.8 80.6 168.62
  • Example 3 48.4 81.9 169.21
  • Example 4 50.1 85.6 170.86
  • Example 5 48.4 84 173.55
  • Example 6 48.9 85.1 174.03
  • Example 7 49.8 87.4 175.50
  • Example 8 51.4 91.7 178.40
  • Example 9 48.1 81.1 168.61
  • Example 10 50.1 87.5 174.65
  • Example 11 47.2 78.8 166.95
  • Example 12 48.1 83.4 173.39
  • Example 13 47.9 80.8 168.68
  • Example 14 48.2 82.1 170.33
  • the first cycle was charged and discharged at 0.1C, and the subsequent cycle was charged and discharged at 0.5C.
  • the thickness change rate was compared with the electrode thickness before the first cycle after disassembling each of the lithium secondary batteries in the state of charge of the 300th cycle and measuring the electrode thickness. The results are shown in Tables 7 and 8.
  • Thickness change rate electrode thickness at 300th cycle of charge state-electrode thickness before first cycle) / electrode thickness before first cycle x 100
  • Example 1 107.24
  • Example 2 107.66
  • Example 3 108.18
  • Example 4 109.14
  • Example 5 108.53
  • Example 6 108.75
  • Example 7 109.09
  • Example 8 110.24
  • Example 9 108.19
  • Example 10 109.23
  • Example 11 108.36
  • Example 12 109.98
  • Example 13 108.96
  • Example 14 108.78
  • Example 15 113.21
  • Example 16 117.25
  • Example 17 114.12
  • Example 18 118.29
  • the secondary battery of the embodiment of the present invention is significantly superior to the secondary battery in terms of high temperature, low temperature life characteristics, high temperature storage characteristics, and thickness change rates in comparison with the comparative examples.
  • Ethylene carbonate (EC): ethyl methyl carbonate (EMC): diethyl carbonate (DEC) 30:50:20 (volume ratio)
  • a non-aqueous organic solvent, LiPF 6 as a lithium salt based on the total amount of the non-aqueous electrolyte solution 1.15 mole / l was added, and 0.5% by weight of cesium bis (trifluoromethanesulfonyl) imide and 1% by weight of lithium difluoro bisoxalatophosphate (weight ratio 1: 2) were added as a additive based on the total amount of the non-aqueous electrolyte solution.
  • NMP solvent N-methyl-2-pyrrolidone
  • the positive electrode mixture slurry was applied to a thin film of aluminum (Al), which is a positive electrode current collector having a thickness of about 20 ⁇ m, dried to prepare a positive electrode, and then subjected to roll press to prepare a positive electrode.
  • a negative electrode mixture slurry was prepared by adding carbon powder as a negative electrode active material, PVdF as a binder, and carbon black as a conductive agent at 96 wt%, 3 wt%, and 1 wt%, respectively, to NMP as a solvent.
  • the negative electrode mixture slurry was applied to a copper (Cu) thin film, which is a negative electrode current collector having a thickness of 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
  • Cu copper
  • the electrolyte solution additive contained 0.5 wt% cesium bis (trifluoromethanesulfonyl) imide and 0.5 wt% lithium difluoro bisoxalatophosphate (weight ratio 1: 1).
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • Example 19 Same as Example 19, except that 0.5 wt% cesium bis (trifluoromethanesulfonyl) imide and 2 wt% lithium difluoro bisoxalato phosphate (weight ratio 1: 4) were included as the electrolyte additive.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • Example 19 Same as Example 19, except that 0.5 wt% of rubidium bis (trifluoromethanesulfonyl) imide and 1 wt% of lithium difluoro bisoxalato phosphate (weight ratio 1: 2) were included as the electrolyte additive.
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • the electrolyte solution additive contained 0.5 wt% cesium bis (trifluoromethanesulfonyl) imide and 0.25 wt% lithium difluoro bisoxalato phosphate (weight ratio 1: 0.5)
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • the electrolyte solution additive contained 0.5 wt% cesium bis (trifluoromethanesulfonyl) imide and 2.25 wt% lithium difluoro bisoxalato phosphate (weight ratio 1: 4.5).
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • the electrolyte solution additive contained 0.5 wt% cesium bis (fluorosulfonyl) imide and 0.5 wt% lithium difluoro bisoxalato phosphate (weight ratio 1: 1).
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • the lithium secondary batteries of Example 1, Examples 19 to 25, and Comparative Example 1 were stored at 60 ° C., and then output was calculated using a voltage difference generated by discharging at SOC at 50% for 5 seconds at 50% of SOC. The result is shown in FIG.

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Abstract

La présente invention peut fournir un additif d'électrolyte comprenant un sel d'un anion, dérivé d'un composé contenant un atome d'azote, et Cs+ ou Rb+. La présente invention peut également fournir un additif d'électrolyte comprenant en outre du difluorobisoxalatophosphate de lithium. La présente invention concerne un électrolyte non aqueux comprenant un sel de lithium, un solvant organique non aqueux et l'additif d'électrolyte et peut fournir une batterie secondaire au lithium comprenant : une électrode positive comprenant un matériau actif positif ; une électrode négative comprenant un matériau actif négatif ; un séparateur intercalé entre l'électrode positive et l'électrode négative ; et l'électrolyte non aqueux.
PCT/KR2017/009758 2016-09-07 2017-09-06 Additif d'électrolyte et batterie secondaire au lithium le comprenant Ceased WO2018048188A1 (fr)

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CN201780055004.1A CN109690864A (zh) 2016-09-07 2017-09-06 电解液添加剂和包含该电解液添加剂的锂二次电池
JP2019513038A JP2019526914A (ja) 2016-09-07 2017-09-06 電解液添加剤及びこれを含むリチウム二次電池
EP17849072.8A EP3512024A4 (fr) 2016-09-07 2017-09-06 Additif d'électrolyte et batterie secondaire au lithium le comprenant
US16/293,685 US11024881B2 (en) 2016-09-07 2019-03-06 Electrolyte additive and lithium secondary battery comprising same

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KR10-2016-0115146 2016-09-07
KR20160115146 2016-09-07
KR1020160174854A KR20180027987A (ko) 2016-09-07 2016-12-20 전해액 첨가제 및 이를 포함하는 리튬 이차 전지
KR10-2016-0174854 2016-12-20
KR1020170081412A KR101980315B1 (ko) 2016-09-07 2017-06-27 전해액 첨가제 및 이를 포함하는 리튬 이차 전지
KR10-2017-0081412 2017-06-27

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CN113921824A (zh) * 2021-10-12 2022-01-11 松山湖材料实验室 锂离子二次电池

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KR20140039234A (ko) * 2011-05-24 2014-04-01 시온 파워 코퍼레이션 전기화학 전지, 그의 구성성분, 및 그의 제조 및 사용 방법
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CN113921824A (zh) * 2021-10-12 2022-01-11 松山湖材料实验室 锂离子二次电池

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