WO2019049775A1 - Composé de sulfate de lithium-bore, additif pour batterie secondaire au lithium, solution électrolytique non aqueuse pour batterie, et batterie secondaire au lithium - Google Patents

Composé de sulfate de lithium-bore, additif pour batterie secondaire au lithium, solution électrolytique non aqueuse pour batterie, et batterie secondaire au lithium Download PDF

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WO2019049775A1
WO2019049775A1 PCT/JP2018/032272 JP2018032272W WO2019049775A1 WO 2019049775 A1 WO2019049775 A1 WO 2019049775A1 JP 2018032272 W JP2018032272 W JP 2018032272W WO 2019049775 A1 WO2019049775 A1 WO 2019049775A1
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lithium
battery
group
carbonate
formula
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Japanese (ja)
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涵 張
雄介 清水
後藤　謙一
三尾　茂
仁志 大西
玄 宮田
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三井化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/14—Compounds containing boron and nitrogen, phosphorus, sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/02—Lithium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • 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
    • 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 disclosure relates to a novel lithium boron sulfate compound, an additive for a lithium secondary battery, a non-aqueous electrolyte for a battery, and a lithium secondary battery.
  • Boron compounds are used, for example, in the field of electrochemistry.
  • a non-aqueous electrolyte for a lithium secondary battery containing a borate ester selected from the group consisting of alkyl borate esters and halogen-containing borate esters is known (see, for example, Patent Document 1).
  • Non-aqueous electrolytes containing organic boron compounds having a specific structure are known (see, for example, Patent Document 2).
  • a non-aqueous electrolytic solution battery comprising a non-aqueous electrolytic solution containing a boronic acid ester and / or a borinic acid ester (see, for example, Patent Document 3).
  • lithium batteries, lithium ion batteries, as an electrolyte for electrochemical devices such as an electric double layer capacitor compounds such as LiBF 3 (PO 2 F 2) has been known (e.g., see Patent Document 4).
  • a compound such as CH 3 SO 3 BF 3 Li is known as an electrolyte used for a non-aqueous electrolyte solution of a storage device such as a lithium secondary battery (see, for example, Patent Document 5).
  • Patent Document 1 Patent No. 4187959
  • Patent Document 2 Japanese Patent Application Laid-Open No. 11-3728
  • Patent Document 3 Patent No. 3439002
  • Patent Document 4 Patent No. 5544748
  • Patent Document 5 Patent No. 6075374
  • An object of the present disclosure is to provide a novel lithium boron sulfate compound, an additive for a lithium secondary battery containing the lithium boron sulfate compound, a non-aqueous electrolyte for battery that can reduce battery resistance and improve battery life, And providing a lithium secondary battery with reduced battery resistance and improved battery life.
  • Means for solving the above problems include the following aspects.
  • R 0 represents an alkoxy group having 1 to 20 carbon atoms or a group represented by formula (II).
  • * represents a bonding position.
  • a non-aqueous electrolytic solution for battery comprising the lithium boron sulfate compound according to any one of ⁇ 1> to ⁇ 3>.
  • R c1 and R c2 each independently represent a hydrogen atom, a methyl group, an ethyl group or a propyl group.
  • ⁇ 7> positive electrode Lithium metal, lithium-containing alloy, metal or alloy capable of alloying with lithium, oxide capable of doping and dedoping lithium ion, transition metal nitride capable of doping and dedoping lithium ion, lithium
  • a negative electrode including, as a negative electrode active material, at least one selected from the group consisting of carbon materials capable of ion doping and dedoping;
  • a novel lithium boron sulfate compound, a lithium secondary battery additive containing the lithium boron sulfate compound, a non-aqueous electrolyte for battery that can reduce battery resistance and improve battery life, And a lithium secondary battery with reduced battery resistance and improved battery life.
  • FIG. 1 is a schematic perspective view showing an example of a laminate type battery, which is an example of a lithium secondary battery of the present disclosure.
  • FIG. 2 is a schematic cross-sectional view in the thickness direction of the laminated electrode body accommodated in the laminate type battery shown in FIG. It is a schematic sectional drawing which shows an example of a coin-type battery which is another example of the lithium secondary battery of this indication.
  • a numerical range represented using “to” means a range including numerical values described before and after “to” as the lower limit value and the upper limit value.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless a plurality of substances corresponding to each component are present in the composition.
  • the lithium boron sulfate compound of the present disclosure is a lithium boron sulfate compound represented by the following formula (I).
  • R 0 represents an alkoxy group having 1 to 20 carbon atoms or a group represented by formula (II).
  • * represents a bonding position.
  • the lithium boron sulfate compound of the present disclosure is a novel compound different from conventional boron compounds.
  • Patent Document 5 discloses compounds such as CH 3 SO 3 BF 3 Li.
  • Compounds of CH like 3 SO 3 BF 3 Li described in Patent Document 5 a compound having an SO 3 group, i.e., while the sulfonic acid lithium borohydride, compounds of the present disclosure, boron sulphate having SO 4 group It differs in that it is a lithium compound.
  • the alkoxy group having 1 to 20 carbon atoms represented by R 0 may be substituted by an unsubstituted alkoxy group having 1 to 20 carbon atoms and a fluorine atom having 1 to 20 carbon atoms A good alkoxy group is mentioned.
  • the carbon number of the alkoxy group having 1 to 20 carbon atoms represented by R 0 is preferably 1 to 12, more preferably 1 to 6, and still more preferably 1 or 2.
  • the alkoxy group having 1 to 20 carbon atoms represented by R 0 may be a linear alkoxy group, a branched alkoxy group, or a cyclic alkoxy group. .
  • the alkoxy group having 1 to 20 carbon atoms represented by R 0 may be substituted by a fluorine atom.
  • a C1-C20 alkoxy group in R 0 Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, 1-ethylpropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, 2-methylbutoxy group, 3, 3-dimethyl Butoxy group, n-pentyloxy group, isopentyloxy group, neopentyloxy group, 1-methylpentyloxy group, n-hexyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, n -Heptyloxy, isoheptyloxy, sec-heptyloxy, tert-heptyloxy, n-octyloxy, isooctyloxy, sec-octyloxy, tert-octyloxy, nonyloxy, de
  • the alkoxy group having 1 to 20 carbon atoms represented by R 0 is preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group or an n-butoxy group, more preferably a methoxy group or an ethoxy group.
  • R 0 a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group or a group represented by the above formula (II) is preferable.
  • lithium boron sulfate compounds represented by the formula (I) include compounds represented by the following formula (I-1), the following formula (I-2), or the following formula (I-3) .
  • the lithium boron sulfate compound represented by the formula (I) is not limited to these specific examples.
  • Production method X is a lithium lithium boron sulfate compound of the present disclosure (ie, a compound of the present disclosure) by reacting a lithium sulfate salt compound optionally having an alkyl group having 1 to 20 carbon atoms with a boron trifluoride compound in a solvent. And a reaction step of obtaining a lithium boron sulfate compound represented by the formula (I); hereinafter, also simply referred to as "lithium lithium sulfate compound”.
  • the lithium sulfate salt compound in the reaction step has, for example, lithium sulfate; lithium methyl sulfate, lithium ethyl sulfate, lithium propyl sulfate, lithium isopropyl sulfate, lithium n-butyl sulfate, lithium octyl sulfate, lithium dodecyl sulfate, etc. And lithium sulfate compounds having an alkyl group of -20. Among them, lithium sulfate, methyl lithium sulfate or lithium ethyl sulfate is preferable.
  • gaseous trifluoride boron and a boron trifluoride complex are mentioned.
  • the boron trifluoride complex include boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex, boron trifluoride dimethyl ether complex, boron trifluoride dibutyl ether complex and the like, and boron trifluoride diethyl ether Complexes are preferred.
  • Examples of the solvent in the reaction step include acetone, ethyl acetate, acetonitrile, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, hexane, heptane, octane, nonane, decane, toluene, xylene (ortho, meta, para), ethylbenzene, butyl Non-aqueous solvents such as benzene, pentylbenzene, hexylbenzene, heptylbenzene, propylbenzene, isopropylbenzene (cumene), cyclohexylbenzene, tetralin, mesitylene methylcyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane, cyclononane .
  • the reaction in the reaction step can be carried out under normal pressure or reduced pressure.
  • the reaction in the reaction step is preferably carried out under an inert atmosphere (for example, under a nitrogen atmosphere, under an argon atmosphere, etc.) from the viewpoint of preventing the mixing of components (for example, water) that inhibit the formation of the lithium boron sulfate compound.
  • the reaction temperature in the reaction step is preferably 20 ° C. to 150 ° C., more preferably 40 ° C. to 120 ° C., and still more preferably 60 ° C. to 100 ° C.
  • the reaction temperature is 20 ° C. or more, the formation of a lithium boron sulfate compound is likely to be promoted.
  • the reaction temperature is 150 ° C. or less, the decomposition of the produced lithium boron sulfate compound is suppressed, and the production rate is likely to be improved.
  • the reaction time in the reaction step is preferably 30 minutes to 12 hours, and more preferably 1 hour to 8 hours, from the viewpoint of efficiently advancing the reaction between the lithium sulfate salt compound and the boron trifluoride compound. .
  • lithium boron sulfate compound after a reaction process.
  • the solid or liquid may be removed without special treatment.
  • the lithium boron sulfate compound can be taken out by separating the solvent from the slurry and drying it.
  • the lithium boron sulfate compound can be taken out by distilling the solvent out of the solution by heat concentration or the like.
  • a lithium boron sulfate compound is precipitated by adding a solvent in which the lithium boron sulfate compound is not dissolved to the solution.
  • the lithium boron sulfate compound can also be removed by separating the solvent from the solution and drying.
  • the pressure at the time of drying the removed lithium boron sulfate compound may be either normal pressure or reduced pressure.
  • the temperature for drying the lithium lithium borate compound taken out is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 100 ° C., and still more preferably 20 ° C. to 60 ° C. When the temperature is 20 ° C. or more, the drying efficiency is excellent.
  • disassembly of the produced lithium boron sulfate compound is suppressed as temperature is 150 degrees C or less, and it is easy to take out a lithium boron sulfate compound stably.
  • the lithium boron sulfate compound removed may be used as it is, for example, may be dispersed or dissolved in a solvent, or may be used in combination with other solid substances.
  • the lithium boron sulfate compound of the present disclosure is an additive for lithium battery (preferably an additive for lithium secondary battery, more preferably an additive for non-aqueous electrolyte of lithium secondary battery), a reagent, a synthesis reaction catalyst It can be usefully used for applications such as electrolytes for various electrochemical devices, doping agents, and additives for lubricating oils.
  • the additive for a secondary battery of the present disclosure includes the lithium boron sulfate compound described above.
  • the additive for a secondary battery of the present disclosure is particularly suitable as an additive for a non-aqueous electrolyte of a lithium secondary battery.
  • Non-aqueous electrolyte for batteries contains the lithium boron sulfate compound of the present disclosure.
  • the non-aqueous electrolyte of the present disclosure can reduce battery resistance by containing the lithium boron sulfate compound of the present disclosure. Furthermore, the non-aqueous electrolyte of the present disclosure can maintain a high discharge capacity of the battery by containing the lithium boron sulfate compound of the present disclosure.
  • the battery resistance can be reduced compared to the non-aqueous electrolyte containing CH 3 SO 3 BF 3 Li described in Patent Document 5 described above. Excellent. Furthermore, the non-aqueous electrolyte of the present disclosure has higher discharge capacity and discharge capacity retention rate of the battery as compared with the non-aqueous electrolyte containing CH 3 SO 3 BF 3 Li described in Patent Document 5 described above. It is excellent in the effect that it can maintain.
  • the non-aqueous electrolytic solution of the present disclosure may contain only one type of the lithium boron sulfate compound, or may contain two or more types.
  • the content (total content in the case of two or more types) of the lithium boron sulfate compound in the non-aqueous electrolyte of the present disclosure is 0.001% by mass to 10% by mass with respect to the total amount of the non-aqueous electrolyte Is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 5% by mass, and 0.4 to 5% by mass.
  • the amount of the lithium boron sulfate compound may be reduced as compared to the amount added to the non-aqueous electrolyte. Therefore, when the lithium boron sulfate compound can be detected even in a small amount in the non-aqueous electrolyte removed from the battery, it is included in the range of the non-aqueous electrolyte of the present disclosure. In addition, even when the lithium borohydride compound can not be detected from the non-aqueous electrolytic solution, the compound derived from the decomposition product of the lithium borate lithium compound is also detected in the non-aqueous electrolytic solution or in the film of the electrode.
  • non-aqueous electrolyte of the present disclosure The handling is the same for compounds other than the above-mentioned lithium boron sulfate compound that can be contained in the non-aqueous electrolytic solution.
  • the non-aqueous electrolyte generally contains a non-aqueous solvent.
  • Non-aqueous solvent Although various well-known things can be suitably selected as a non-aqueous solvent, It is preferable to use at least one chosen from a cyclic
  • cyclic aprotic solvent cyclic carbonate, cyclic carboxylic acid ester, cyclic sulfone, cyclic ether can be used.
  • the cyclic aprotic solvent may be used alone or in combination of two or more.
  • the mixing ratio of the cyclic aprotic solvent in the nonaqueous solvent is 10% by mass to 100% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 80% by mass. By setting the ratio as such, the conductivity of the electrolytic solution related to the charge and discharge characteristics of the battery can be increased.
  • cyclic carbonates include ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 2,3-pentylene carbonate and the like.
  • ethylene carbonate and propylene carbonate having a high dielectric constant are preferably used.
  • ethylene carbonate is more preferable.
  • cyclic carboxylic acid esters include ⁇ -butyrolactone, ⁇ -valerolactone, and alkyl-substituted products such as methyl ⁇ -butyrolactone, ethyl ⁇ -butyrolactone and ethyl ⁇ -valerolactone.
  • the cyclic carboxylic acid ester has a low vapor pressure, a low viscosity, and a high dielectric constant, and can lower the viscosity of the electrolytic solution without lowering the flash point of the electrolytic solution and the degree of dissociation of the electrolyte. Therefore, the conductivity of the electrolyte, which is an index related to the discharge characteristics of the battery, can be increased without increasing the flammability of the electrolyte. Therefore, when aiming to improve the flash point of the solvent, It is preferable to use a cyclic carboxylic acid ester as the cyclic aprotic solvent. Among cyclic carboxylic acid esters, ⁇ -butyrolactone is most preferred.
  • the cyclic carboxylic acid ester is preferably used in combination with other cyclic aprotic solvents. For example, a mixture of cyclic carboxylic acid ester and cyclic carbonate and / or linear carbonate can be mentioned.
  • cyclic sulfones examples include sulfolane, 2-methylsulfolane, 3-methylsulfolane, dimethylsulfone, diethylsulfone, dipropylsulfone, methylethylsulfone, methylpropylsulfone and the like.
  • Dioxolane can be mentioned as an example of cyclic ether.
  • Linear aprotic solvent As the chain-like aprotic solvent, a chain carbonate, a chain carboxylic acid ester, a chain ether, a chain phosphoric acid ester and the like can be used.
  • the mixing ratio of the chain-like aprotic solvent in the nonaqueous solvent is 10% by mass to 100% by mass, more preferably 20% by mass to 90% by mass, and particularly preferably 30% by mass to 80% by mass.
  • linear carbonates include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl isopropyl carbonate, ethyl propyl carbonate, dipropyl carbonate, methyl butyl carbonate, ethyl butyl carbonate, dibutyl carbonate, methyl pentyl carbonate, Ethyl pentyl carbonate, dipentyl carbonate, methyl heptyl carbonate, ethyl heptyl carbonate, diheptyl carbonate, methyl hexyl carbonate, ethyl hexyl carbonate, dihexyl carbonate, methyl octyl carbonate, ethyl octyl carbonate, dioctyl carbonate, methyl trifluoroethyl carbonate and the like. These linear carbonates may be used as a mixture of two or more.
  • chain carboxylic acid esters include methyl pivalate and the like.
  • chain ether include dimethoxyethane and the like.
  • linear phosphate ester include trimethyl phosphate.
  • the non-aqueous solvent used in the non-aqueous electrolyte of the present disclosure may be used alone or in combination of two or more.
  • the solvents may be mixed and used.
  • the conductivity of the electrolytic solution related to the charge and discharge characteristics of the battery can also be enhanced by the combination of the cyclic carboxylic acid ester and the cyclic carbonate and / or the chain carbonate.
  • combinations of cyclic carbonate and linear carbonate include ethylene carbonate and dimethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate, propylene carbonate and dimethyl carbonate, propylene carbonate and methyl ethyl carbonate, and propylene carbonate Diethyl carbonate, ethylene carbonate and propylene carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate And diethyl carbonate, ethylene carbonate and dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and propylene carbonate and dimethyl carbon
  • the mixing ratio of the cyclic carbonate to the linear carbonate is, in terms of mass ratio, cyclic carbonate: linear carbonate is 5:95 to 80:20, more preferably 10:90 to 70:30, particularly preferably 15:85. It is ⁇ 55: 45.
  • the ratio By setting the ratio as such, the increase in viscosity of the electrolyte can be suppressed, and the degree of dissociation of the electrolyte can be increased, so that the conductivity of the electrolyte related to the charge and discharge characteristics of the battery can be increased.
  • the solubility of the electrolyte can be further enhanced. Therefore, since it can be set as the electrolyte solution excellent in the electrical conductivity in normal temperature or low temperature, the load characteristic of the battery in normal temperature to low temperature can be improved.
  • examples of combinations of cyclic carboxylic acid esters and cyclic carbonates and / or linear carbonates include ⁇ -butyrolactone and ethylene carbonate, ⁇ -butyrolactone and ethylene carbonate and dimethyl carbonate, ⁇ -butyrolactone and ethylene carbonate and methyl ethyl Carbonate, ⁇ -butyrolactone and ethylene carbonate and diethyl carbonate, ⁇ -butyrolactone and propylene carbonate, ⁇ -butyrolactone and propylene carbonate and dimethyl carbonate, ⁇ -butyrolactone and propylene carbonate and methyl ethyl carbonate, ⁇ -butyrolactone and propylene carbonate and diethyl carbonate, ⁇ -butyrolactone, ethylene carbonate and propylene carbonate, ⁇ -butyrolactone Ethylene carbonate and propylene carbonate and dimethyl carbonate, ⁇ -butyrolactone and ethylene carbonate and propylene carbonate,
  • non-aqueous solvent As the non-aqueous solvent, other solvents other than the above may also be mentioned.
  • amides such as dimethylformamide, linear carbamates such as methyl-N, N-dimethylcarbamate, cyclic amides such as N-methylpyrrolidone, N, N-dimethylimidazolidinone and the like
  • examples include cyclic urea, trimethyl borate, triethyl borate, tributyl borate, trioctyl borate, boron compounds such as trimethylsilyl borate, and polyethylene glycol derivatives represented by the following general formula.
  • the non-aqueous electrolyte of the present disclosure may contain various known electrolytes. Any electrolyte can be used as long as it is usually used as an electrolyte for non-aqueous electrolytes. As an electrolyte, a lithium salt is preferable.
  • R 11 to R 17 are a C 1-8 perfluoroalkyl group.
  • R 11 to R 13 may be identical to or different from one another.
  • R 14 and R 15 may be identical to or different from each other.
  • R 16 and R 17 may be identical to or different from each other.
  • LiPF 6 LiPF 6 , LiBF 4 and LiN (SO 2 C k F (2k + 1 ) 2 ) 2 (k is an integer of 1 to 8) are preferable.
  • the lithium salt concentration of the non-aqueous electrolyte of the present disclosure is preferably 0.1 mol / L to 3 mol / L, and more preferably 0.5 mol / L to 2 mol / L.
  • the lithium salts may be used alone or in combination of two or more.
  • the non-aqueous electrolytic solution of the present disclosure may further contain an additive C which is a compound represented by the following formula (C).
  • R c1 and R c2 each independently represent a hydrogen atom, a methyl group, an ethyl group or a propyl group.
  • R c1 and R c2 each independently represent a hydrogen atom, a methyl group, an ethyl group or a propyl group.
  • Examples of the compound represented by the formula (C) include vinylene carbonate, methylvinylene carbonate, ethylvinylene carbonate, bropyruvylene carbonate, dimethylvinylene carbonate, diethylvinylene carbonate, dipropylvinylene carbonate and the like.
  • vinylene carbonate in the formula (C), a compound in which R c1 and R c2 are both hydrogen atoms is particularly preferable.
  • the content of the additive C (total content when the additive C is a compound of two or more types) is relative to the total amount of the non-aqueous electrolyte 0.001% by mass to 10% by mass is preferable, 0.001% by mass to 5% by mass is more preferable, and 0.001% by mass to 3% by mass is more preferable, and 0.01% by mass to 5% by mass %, More preferably 0.1 to 3% by mass.
  • the non-aqueous electrolyte solution of the present disclosure is not only suitable as a non-aqueous electrolyte solution for batteries, but also for non-aqueous electrolyte solutions for primary batteries and secondary batteries, non-aqueous electrolyte solutions for electrochemical capacitors, electricity It can also be used as an electrolyte solution for multilayer capacitors and aluminum electrolytic capacitors.
  • the lithium secondary battery of the present disclosure includes a positive electrode, a negative electrode, and the non-aqueous electrolyte of the present disclosure. According to the lithium secondary battery of the present disclosure, battery resistance is reduced by including the non-aqueous electrolyte of the present disclosure.
  • the negative electrode may include a negative electrode active material and a negative electrode current collector.
  • the negative electrode active material in the negative electrode metal lithium, lithium-containing alloy, metal or alloy capable of alloying with lithium, oxide capable of doping / dedoping lithium ion, capable of doping / dedoping lithium ion
  • At least one selected from the group consisting of transition metal nitrides and carbon materials capable of doping and de-doping lithium ions (may be used alone or as a mixture containing two or more of these) Good) can be used.
  • metals or alloys that can be alloyed with lithium (or lithium ion) include silicon, silicon alloys, tin, tin alloys and the like.
  • lithium titanate may be used.
  • carbon materials capable of doping and dedoping lithium ions are preferable.
  • examples of such carbon materials include carbon black, activated carbon, graphite materials (artificial graphite, natural graphite), amorphous carbon materials, and the like.
  • the form of the carbon material may be any of fibrous, spherical, potato-like, and flake-like forms.
  • amorphous carbon material examples include hard carbon, coke, mesocarbon microbeads (MCMB) calcined to 1500 ° C. or less, mesophase pitch carbon fiber (MCF) and the like.
  • MCMB mesocarbon microbeads
  • MCF mesophase pitch carbon fiber
  • These carbon materials may be used alone or in combination of two or more.
  • a carbon material having an interplanar spacing d (002) of (002) plane of 0.340 nm or less measured by X-ray analysis is particularly preferable.
  • graphite having a true density of 1.70 g / cm 3 or more or a highly crystalline carbon material having a property close thereto is also preferable. The use of the above carbon materials can increase the energy density of the battery.
  • the negative electrode current collector include metal materials such as copper, nickel, stainless steel, and nickel plated steel. Among them, copper is particularly preferred in view of processability.
  • the positive electrode may include a positive electrode active material and a positive electrode current collector.
  • Polyaniline Li thiophene, polypyrrole, polyacetylene, polyacene, dimercaptothiadiazoles, conductive polymer materials such as polyaniline complex thereof.
  • complex oxides composed of lithium and a transition metal are particularly preferable.
  • the negative electrode is lithium metal or lithium alloy
  • a carbon material can also be used as the positive electrode.
  • a mixture of a composite oxide of lithium and a transition metal and a carbon material can be used as the positive electrode.
  • the positive electrode active material may be used alone or in combination of two or more. When the positive electrode active material is insufficient in conductivity, it can be used together with a conductive aid to form a positive electrode.
  • a conductive support agent carbon materials, such as carbon black, an amorphous whisker, and a graphite, can be illustrated.
  • the positive electrode current collector include metal materials such as aluminum, aluminum alloy, stainless steel, nickel, titanium and tantalum; carbon materials such as carbon cloth and carbon paper; and the like.
  • the lithium secondary battery of the present disclosure preferably includes a separator between the negative electrode and the positive electrode.
  • the separator is a film that electrically insulates the positive electrode and the negative electrode and transmits lithium ions, and examples thereof include porous films and polymer electrolytes.
  • a microporous polymer film is preferably used as the porous membrane, and examples of the material include polyolefin, polyimide, polyvinylidene fluoride, polyester and the like.
  • porous polyolefins are preferable, and specifically, porous polyethylene films, porous polypropylene films, or multilayer films of porous polyethylene films and polypropylene films can be exemplified.
  • the polymer electrolyte may, for example, be a polymer in which a lithium salt is dissolved, or a polymer swollen in an electrolytic solution.
  • the non-aqueous electrolyte of the present disclosure may be used for the purpose of swelling a polymer to obtain a polymer electrolyte.
  • the lithium secondary battery of the present disclosure can take various known shapes, and can be formed into a cylindrical, coin, square, laminate, film, or any other shape.
  • the basic structure of the battery is the same regardless of the shape, and design changes can be made according to the purpose.
  • FIG. 1 is a schematic perspective view showing an example of a laminate type battery which is an example of the lithium secondary battery of the present disclosure
  • FIG. 2 is a thickness of a laminate type electrode body accommodated in the laminate type battery shown in FIG. It is a schematic sectional drawing of a direction.
  • the laminate type battery shown in FIG. 1 the non-aqueous electrolyte (not shown in FIG. 1) and the laminated electrode body (not shown in FIG. 1) are housed inside, and the peripheral portion is sealed.
  • the laminated exterior body 1 by which the inside was sealed is provided.
  • the laminate case 1 for example, a laminate case made of aluminum is used.
  • the laminate type electrode body housed in the laminate outer package 1 is, as shown in FIG. 2, a laminate in which the positive electrode plate 5 and the negative electrode plate 6 are alternately laminated via the separator 7, and And a separator 8 surrounding the periphery.
  • the non-aqueous electrolytic solution of the present disclosure is impregnated in the positive electrode plate 5, the negative electrode plate 6, the separator 7, and the separator 8.
  • the plurality of positive electrode plates 5 in the laminated electrode assembly are all electrically connected to the positive electrode terminal 2 through the positive electrode tab (not shown), and a part of the positive electrode terminal 2 is the laminate case 1. Projecting outward from the peripheral edge ( Figure 1). A portion where the positive electrode terminal 2 protrudes at the peripheral end of the laminate outer package 1 is sealed by an insulating seal 4.
  • each of the plurality of negative electrode plates 6 in the laminated electrode assembly is electrically connected to the negative electrode terminal 3 through the negative electrode tab (not shown), and a part of the negative electrode terminal 3 is in the laminate exterior It protrudes outward from the peripheral end of the body 1 (FIG. 1).
  • the part where the negative electrode terminal 3 protrudes at the peripheral end of the laminate outer package 1 is sealed by an insulating seal 4.
  • the number of the positive electrode plates 5 is five
  • the number of the negative electrode plates 6 is six
  • the positive electrode plate 5 and the negative electrode plate 6 have the separator 7 interposed therebetween.
  • the outer layers are all stacked in an arrangement to be the negative electrode plate 6.
  • the number of positive electrode plates, the number of negative electrode plates, and the arrangement of the laminate type battery are not limited to this example, and various modifications may be made.
  • the laminated electrode body accommodated in the laminate outer package 1 is a laminated electrode body in which one positive electrode plate 5 and one negative electrode plate 6 are laminated via one separator 7. Good.
  • FIG. 3 is a schematic perspective view showing an example of a coin-type battery which is another example of the lithium secondary battery of the present disclosure.
  • a disk-shaped negative electrode 12 a separator 15 into which a non-aqueous electrolyte is injected
  • a disk-shaped positive electrode 11 disk-shaped positive electrode 11
  • spacer plates 17 and 18 of stainless steel or aluminum, etc.
  • the positive electrode can 13 hereinafter also referred to as “battery can”
  • the sealing plate 14 hereinafter also referred to as “battery can lid”.
  • the positive electrode can 13 and the sealing plate 14 are crimped and sealed via the gasket 16.
  • the non-aqueous electrolyte of the present disclosure can be used as the non-aqueous electrolyte to be injected into the separator 15.
  • the lithium secondary battery of the present disclosure is obtained by charging and discharging a lithium secondary battery (lithium secondary battery before charge and discharge) including a negative electrode, a positive electrode, and the non-aqueous electrolyte of the present disclosure.
  • a lithium secondary battery lithium secondary battery before charge and discharge
  • a lithium secondary battery before charge and discharge including the negative electrode, the positive electrode, and the non-aqueous electrolyte of the present disclosure is manufactured, and then, before the charge and discharge.
  • It may be a lithium secondary battery (charged / discharged lithium secondary battery) manufactured by charging / discharging the lithium secondary battery one or more times.
  • the application of the lithium secondary battery of the present disclosure is not particularly limited, and can be used for various known applications.
  • wt% represents mass%.
  • the “added amount” represents the content in the finally obtained non-aqueous electrolyte (that is, the amount relative to the total amount of the finally obtained non-aqueous electrolyte).
  • Example 1 Synthesis of a Compound Represented by Formula (I-1)
  • a 50 mL flask equipped with a stirrer, a thermometer, a gas inlet line, and an exhaust line was purged with dry nitrogen gas, and then dimethyl dimethyl ether was added thereto.
  • 7.5 g of carbonate (solvent) and 2.41 g (0.017 mol) of boron trifluoride diethyl etherate were added and mixed by stirring at room temperature (25 ° C., the same shall apply hereinafter) to obtain a mixed liquid .
  • To the resulting mixture 2.01 g (0.017 mol) of lithium lithium sulfate was added, and the resulting liquid was heated to 90 ° C.
  • reaction step methyl lithium sulfate was completely dissolved in the mixture.
  • the liquid was cooled to room temperature, and then the solvent was distilled off from the liquid under conditions of 10 kPa or less and 30 ° C. The resulting residue was further dried under conditions of 10 kPa or less and 30 ° C. to obtain 3.16 g of a solid product.
  • the differential scanning calorimetry (DSC) measurement from room temperature to 600 degreeC was performed about the obtained solid product.
  • DSC differential scanning calorimetry
  • an endothermic thermal decomposition behavior at 198 ° C. peak was observed, which was not observed when each of boron trifluoride diethyl ether complex and methyl methyl sulfate was measured alone.
  • the endothermic thermal decomposition behavior was observed using a differential scanning calorimeter (DSC 220 C type) manufactured by Seiko Instruments Inc. The same applies to the following.
  • Example 1 From the above results, in Example 1, it was confirmed that the compound represented by Formula (I-1), which is a specific example of the compound represented by Formula (I), was generated by the following reaction scheme. .
  • Example 2 Synthesis of a Compound Represented by Formula (I-3)
  • 15 g of carbonate (solvent) and 2.55 g (0.018 mol) of boron trifluoride diethyl etherate were added and mixed by stirring at room temperature to obtain a mixed solution.
  • 0.99 g (0.009 mol) of lithium sulfate was added, and the obtained liquid was heated to 90 ° C. with stirring, and stirred at a liquid temperature of 90 ° C. under solvent reflux for 3 hours (Reaction process).
  • the liquid after stirring for 3 hours was cooled to room temperature, and then the liquid was filtered to remove insoluble components from the liquid.
  • the solvent was distilled off from the obtained filtrate under the conditions of a pressure of 10 kPa or less and a temperature of 30 ° C.
  • the remaining residue was further dried under conditions of a pressure of 10 kPa or less and a temperature of 30 ° C. to obtain 2.08 g of a solid product.
  • a 3.9 mg sample is taken from the obtained solid product, and the taken sample is dissolved in a heavy dimethyl sulfoxide solvent together with 6.5 mg (0.04 mmol) of trifluoromethylbenzene as an internal standard substance, and the obtained sample
  • the solutions were each subjected to 19 F-NMR analysis and 11 B-NMR analysis.
  • the chemical shifts [ppm] of the spectra obtained by each of 19 F-NMR analysis and 11 B-NMR analysis were as follows.
  • the integral value of the spectrum of the sample when the integral value of the spectrum of the internal standard substance was 30 F was as follows.
  • the 19 F-NMR and 11 B-NMR confirmed a spectrum derived from the fluoroborane skeleton. Based on the relationship between the mass of each of the sample and internal standard substance and the spectral integration value of each of the sample and internal standard substance in 19 F-NMR analysis, the formula (I ⁇ ) in the sample (ie, solid product) was determined. As a result, the purity was 99.4%.
  • Example 2 it was confirmed that the compound represented by Formula (I-3), which is a specific example of the compound represented by Formula (I), was generated by the following reaction scheme. .
  • the compounds obtained in each example were identified chemical composition by NMR analysis, and endothermic thermal decomposition behavior not observed in the starting compounds was observed. That is, it was confirmed that the compounds obtained in the respective examples were not mere mixtures of the compounds of the respective raw materials, but were novel lithium boron sulfate compounds having thermal properties different from them.
  • Example 101 The coin-type battery which is a lithium secondary battery was produced in the following procedures. ⁇ Fabrication of negative electrode> 100 parts by mass of natural graphite-based graphite, 1 part by mass of carboxymethyl cellulose and 2 parts by mass of SBR latex were kneaded with an aqueous solvent to prepare a paste-like negative electrode mixture slurry. Next, this negative electrode material mixture slurry is applied to a negative electrode current collector made of a 18 ⁇ m thick copper foil and dried, and then compressed by a roll press to form a sheet comprising the negative electrode current collector and the negative electrode active material layer. The negative electrode was obtained. The application density of the negative electrode active material layer at this time was 12 mg / cm 2 , and the packing density was 1.5 g / mL.
  • the coating density of the positive electrode active material layer at this time was 22 mg / cm 2 , and the packing density was 2.9 g / mL.
  • a mixed solvent was obtained by mixing ethylene carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) as non-aqueous solvents.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • EMC methyl ethyl carbonate
  • the LiPF 6 as the electrolyte
  • electrolyte concentration in the non-aqueous electrolyte solution obtained was dissolved at a 1 mol / L.
  • a mixture of the compound (additive) represented by the above-mentioned formula (I-1) and DMC was added to obtain a non-aqueous electrolyte.
  • the addition amount of the compound represented by the formula (I-1) (that is, the content with respect to the total amount of the final non-aqueous electrolyte) was 0.2 mass%.
  • the above-mentioned negative electrode was punched out in a disk shape with a diameter of 14.5 mm and the above-mentioned positive electrode with a diameter of 13 mm to obtain coin-shaped electrodes (a negative electrode and a positive electrode). Further, a microporous polyethylene film having a thickness of 20 ⁇ m was punched into a disk shape having a diameter of 16 mm to obtain a separator.
  • the obtained coin-like negative electrode, separator and coin-like positive electrode are stacked in this order in a stainless steel battery can (2032 size), and 40 ⁇ l of the above non-aqueous electrolyte is injected to the separator, positive electrode and negative electrode. I let it go.
  • the above coin-type battery was CC-CV charged at a charge rate of 0.2 C to 4.2 V at 25 ° C. in a thermostat, and then CC discharge at a discharge rate of 0.2 C was repeated four times.
  • Initial discharge capacity maintenance rate (Initial discharge capacity maintenance rate (0.2C-2C)) The initial discharge capacity (2 C) was measured in the same manner as the initial discharge capacity (0.2 C) except that the discharge rate was changed from 0.2 C to 2 C.
  • the initial discharge capacity retention rate (0.2C-2C) was determined based on the following equation.
  • Initial discharge capacity retention rate (0.2C-2C) (initial discharge capacity (2C)) / (initial discharge capacity (0.2C))
  • the initial discharge capacity retention ratio (0.2C-2C) of the coin-type battery was similarly determined for Comparative Example 101 described later. As a relative value when the initial discharge capacity retention rate (0.2C-2C) of the coin-type battery in Comparative Example 101 is 100, the initial discharge capacity retention rate (0.2C- of the coin-type battery in Example 101) 2C) (relative value) was determined. The results are shown in Table 1.
  • the discharge capacity (2 C) after the low temperature cycle was measured in the same manner as the discharge capacity (0.2 C) after the low temperature cycle except that the discharge rate was changed from 0.2 C to 2 C.
  • the discharge capacity retention ratio (0.2C-1C) after the high temperature cycle of the coin battery was similarly determined for Comparative Example 101 described later.
  • the discharge capacity retention ratio of the coin-type battery in Example 101 after the high temperature cycle as a relative value when the discharge capacity retention ratio (0.2 C-1 C) after the high temperature cycle of the coin battery in Comparative Example 101 is 100 ( 0.2C-1C) (relative value) was determined. The results are shown in Table 1.
  • Initial cell resistance was measured at 25 ° C. by the following method using the coin-type battery after conditioning. First, CC 10 s was discharged at a discharge rate of 0.2 C from 50% of SOC (abbreviation of State of Charge), and CC-CV 10 s was performed at a charge rate of 0.2 C. Next, CC 10s discharge was performed at a discharge rate 1C, and CC-CV 10s charging was performed at a charge rate 1C. Next, CC 10 s was discharged at a discharge rate 2 C, and CC-CV 10 s was charged at a charge rate 2 C.
  • SOC abbreviation of State of Charge
  • CC 10 s was discharged at a discharge rate of 5 C, and CC-CV 10 s charging was performed at a charge rate of 5 C.
  • CC10s discharge means discharging for 10 seconds by a constant current (Constant Current).
  • the CC-CV 10 s charging means charging for 10 seconds at a constant current and constant voltage.
  • the direct current resistance was determined from each charge and discharge rest current and each charge and discharge rest voltage, and the obtained direct current resistance was taken as the initial cell resistance of the coin-type battery.
  • the initial battery resistance of the coin battery was determined in the same manner for Comparative Example 101 described later.
  • the initial cell resistance (relative value) of the coin-type battery in Example 101 was determined as a relative value when the initial cell resistance of the coin-type battery in Comparative Example 101 was 100. The results are shown in Table 1.
  • the battery resistance after the low temperature cycle was measured by the method similar to the initial stage direct current resistance using the coin type battery after the low temperature cycle test.
  • the battery resistance of the coin battery after the low temperature cycle was measured in the same manner as in Comparative Example 101 described later.
  • the battery resistance (relative value) after the low temperature cycle of the coin battery in Example 101 was determined as a relative value when the battery resistance after the low temperature cycle of the coin battery in Comparative Example 101 was 100. The results are shown in Table 1.
  • the battery resistance after the high temperature cycling was measured by the method similar to the initial stage direct current resistance using the coin type battery after the high temperature cycle test.
  • the battery resistance of the coin battery after the high temperature cycle was measured in the same manner as in Comparative Example 101 described later.
  • the battery resistance (relative value) after the high temperature cycle of the coin battery in Example 101 was determined as a relative value when the battery resistance after the high temperature cycle of the coin battery in Comparative Example 101 was 100. The results are shown in Table 1.
  • Example 102 The addition amount of the compound represented by the formula (I-1) is 0.5 mass% (Example 102), 1.0 mass% (Example 103), and 1.5 mass% (Example 104). The same operation as in Example 101 was performed except that each was changed. The results are shown in Table 1.
  • Example 105 The compound represented by the formula (I-1) used for the preparation of the non-aqueous electrolyte (addition amount: 0.2% by mass) was added to the compound represented by the formula (I-3) described above (addition amount: 0.5) The same operation as in Example 101 was carried out except that it was changed to% by mass. The results are shown in Table 1.
  • Example 106 The same operation as in Example 105 was performed, except that the addition amount of the compound represented by the formula (I-3) was changed to 1.0% by mass. The results are shown in Table 1.
  • Comparative Example 101 The same operation as in Example 101 was performed except that the compound represented by the formula (I-1) was not added. The results are shown in Table 1.
  • Comparative Example 102 The compound represented by the formula (I-1) used in the preparation of the non-aqueous electrolyte (addition amount: 0.2% by mass) is represented by the compound represented by the following formula (C1) (addition amount: 0.5% by mass) The same operation as in Example 101 was performed except that the above was changed to The results are shown in Table 1.
  • Comparative Example 103 The same operation as in Comparative Example 102 was performed except that the addition amount of the compound represented by the above formula (C1) was changed to 1.0% by mass. The results are shown in Table 1.
  • the coin batteries of Examples 101 to 106 have battery resistance (specifically, initial battery resistance, battery resistance after a low temperature cycle, in comparison with the coin batteries of Comparative Examples 101 to 103. And cell resistance after high temperature cycling) was reduced.
  • the coin-type batteries of Examples 101 to 106 are different from the coin-type batteries of Comparative Examples 101 to 103 in the discharge capacity of the battery (specifically, the initial discharge capacity, the initial discharge capacity maintenance rate, and the low temperature cycle It is also excellent in the later discharge capacity maintenance rate and the discharge capacity maintenance rate after the high temperature cycle.
  • Example 201 A coin-type battery was produced in the same manner as in Example 101 except that vinylene carbonate (VC) (addition amount: 1.0 wt%) was further added to the non-aqueous electrolytic solution. With respect to the obtained coin-type battery, the initial discharge capacity (0.2 C), the initial discharge capacity retention rate (0.2 C-2 C), and the discharge capacity retention rate after low temperature cycle (0 2C-2C), discharge capacity retention ratio after high temperature cycle (0.2C-1C), initial cell resistance, cell resistance after low temperature cycle, and cell resistance after high temperature cycle were determined. The coin-type battery was evaluated in the same manner for Comparative Example 201 described later, and the relative value when the result of Comparative Example 201 was 100 was determined.
  • VC vinylene carbonate
  • additive A a lithium boron sulfate compound contained in the non-aqueous electrolytic solution
  • VC vinylene carbonate
  • Example 201 is similar to Example 201 except that the addition amount of the compound represented by the formula (I-1) is changed to 0.5% by mass (Example 202) and 1.0% by mass (Example 203). I did the operation. The results are shown in Table 2.
  • Example 204 The compound represented by the formula (I-1) used for the preparation of the non-aqueous electrolyte (addition amount: 0.2% by mass) was added to the compound represented by the formula (I-3) described above (addition amount: 0.5) The same operation as in Example 201 was carried out except that it was changed to% by mass. The results are shown in Table 2.
  • Example 205 and 206 The same as Example 204 except that the addition amount of the compound represented by Formula (I-3) was changed to 1.0% by mass (Example 205) and 1.5% by mass (Example 206). I did the operation. The results are shown in Table 2.
  • Comparative Example 201 The same operation as in Example 201 was carried out except that the compound represented by the formula (I-1) was not added. The results are shown in Table 2.
  • the coin-type batteries of Examples 201 to 206 have battery resistance (specifically, initial battery resistance, battery resistance after low temperature cycle, and battery resistance after comparison with the coin-type batteries of Comparative Example 201; Battery resistance after high temperature cycling was reduced.
  • the coin-type batteries of Examples 201 to 206 have the discharge capacity of the battery (specifically, the initial discharge capacity, the initial discharge capacity retention rate, and the discharge after the low temperature cycle) as compared with the comparative example 201 coin-type battery.
  • the capacity retention rate and the discharge capacity retention rate after the high temperature cycle were also excellent.

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Abstract

L'invention concerne un composé de sulfate de lithium-bore représenté par la formule (I). Dans la formule (I), R0 représente un groupe alcoxy en C1–20, ou un groupe représenté par la formule (II). Dans la formule (II), * représente une position de liaison.
PCT/JP2018/032272 2017-09-05 2018-08-30 Composé de sulfate de lithium-bore, additif pour batterie secondaire au lithium, solution électrolytique non aqueuse pour batterie, et batterie secondaire au lithium WO2019049775A1 (fr)

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CN112390732A (zh) * 2019-08-19 2021-02-23 杉杉新材料（衢州）有限公司 一种硫酸单烃基酯锂盐衍生物的合成方法
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CN114695960A (zh) * 2020-12-31 2022-07-01 浙江蓝天环保高科技股份有限公司 一种兼具高低温性能的新型添加剂、其制备方法及应用

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CN112349951B (zh) * 2019-08-08 2022-06-03 杉杉新材料（衢州）有限公司 包含含硫锂盐衍生物添加剂的非水电解液及锂离子电池
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