Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0566—Liquid materials
  • H01M10/0567—Liquid materials characterised by the additives
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to an electrolyte additive for a secondary battery, an electrolyte including the same, and a secondary battery.
• lithium secondary batteries that exhibit high energy density and operating potential, and have excellent cycle life and low self discharge rate have been commercialized and widely used.
• Lithium ion secondary batteries are mainly used as power sources of such electric vehicles and hybrid electric vehicles, and researches to improve output stability and energy density of such lithium secondary batteries and corresponding materials are being actively conducted.
• Such a lithium secondary battery is composed of a negative electrode such as a carbon material for adsorbing and releasing lithium ions, a positive electrode made of a lithium-containing oxide, or the like, and a non-aqueous electrolyte solution in which an appropriate amount of lithium salt is dissolved in a mixed organic solvent.
• Korean Patent No. 1486618 discloses that low temperature cycle characteristics can be improved by using an electrolyte solution containing a sulfonic acid phenyl compound
• Korean Patent Publication No. 2015-0050493 discloses a high temperature by adding ethylene sulfate to an electrolyte solution. And improving the output characteristics of the battery at low temperatures.
• 2015-0050082 discloses that it is possible to improve the cycle characteristics of the battery by adding a compound containing a sulfinyl group to the electrolyte solution
• Republic of Korea Patent No. 0976958 uses a sultone compound as an additive
• Japanese Patent No. 4190162 discloses that the high temperature stability of the battery can be improved by using an electrolyte solution containing propenesultone.
• WO 2012-053644 discloses that a high temperature storage capacity of a battery can be maintained by using an electrolyte solution containing a sulfate ester compound.
• the inventors of the present invention have continuously conducted research, and have found a compound capable of improving output characteristics, improving storage characteristics, improving lifetime characteristics, and withstanding voltage characteristics of an electrolyte, and applying the same to a secondary battery electrolyte.
• the invention was completed.
• an object of the present invention to provide an electrolyte additive which is included in an electrolyte for a lithium secondary battery to improve the output characteristics of the battery and lower the electrochemical decomposition of the electrolyte to improve life and storage characteristics.
• Another object of the present invention is to provide a secondary battery electrolyte and a secondary battery including the improved withstand voltage characteristics.
• the present invention provides a secondary battery electrolyte additive containing a compound of formula (1).
• the present invention is a non-aqueous solvent; Lithium salts; And it provides a secondary battery electrolyte comprising the electrolyte additive.
• the present invention provides a secondary battery comprising the secondary battery electrolyte.
• the electrolyte additive for a secondary battery of the present invention can be provided in the electrolyte to provide a secondary battery having excellent physical properties in terms of output characteristics, life characteristics, storage characteristics and withstand voltage characteristics, it can be used for mobile, electric vehicles, power tools, electric It can be usefully used for secondary batteries for bikes, robots or drones.
• the present invention provides a secondary battery electrolyte additive, comprising a compound of formula (1).
• the electrolyte additive for a secondary battery according to the present invention can improve the output performance of the battery by lowering the interfacial resistance of the electrolyte, improve the storage characteristics and life characteristics, enable long-term use of the battery, and improve the withstand voltage characteristics of the electrolyte.
• the compound of Formula 1 is a known compound (CAS No. 496-45-7), bicyclo-glyoxal sulfate, glyoxal sulfate, or 3a, 6a-dihydro- [ 1,3,2] dioxathiolo [4,5-d] [1,3,2] dioxathiol 2,2,5,5-tetraoxide (3a, 6a-dihydro- [1,3,2 ] dioxathiolo [4,5-d] [1,3,2] dioxathiole 2,2,5,5-tetraoxide), etc., and can be purchased commercially.
• the compound of Formula 1 may be prepared by a known synthesis method, for example, 1,1,2,2-tetrachloroethane as a starting material may be prepared by a known synthesis method to react with fuming sulfuric acid and the like ( US Patent No. 1,999,995 and US Patent No. 2,415,397).
• the compound of Formula 1 may be used alone or in combination with a known electrolyte additive commonly used.
• the present invention is a non-aqueous solvent; Lithium salts; And it provides a secondary battery electrolyte comprising a secondary battery electrolyte additive as described above.
• the secondary battery electrolyte may further include a known electrolyte additive commonly used.
• the non-aqueous solvent is a linear or cyclic carbonate solvent or a lactone solvent, and preferably has high solubility in lithium salt and electrolyte additive for a secondary battery.
• the non-aqueous solvent may be diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, Linear carbonate solvents such as ethyl propyl carbonate and methyl ethyl carbonate; Cyclic carbonate solvents such as ethylene carbonate, propylene carbonate, butylene carbonate, and fluoroethylene carbonate;
• it may be one solvent selected from the group consisting of lactone solvents such as gamma-butyrolactone (gamma-butyrolactone) or two or more mixed solvents.
• the non-aqueous solvent may be dehydrated, and specifically, the water content of the non-aqueous solvent may be 150 ppm by weight or less.
• the moisture content of the non-aqueous solvent is 150 ppm by weight or less, the decomposition of lithium salts in the battery and the hydrolysis of the electrolyte additive may be suppressed to further improve the electrolyte performance.
• the lithium salt is to improve the ionic conductivity of the electrolyte, for example, LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2, LiN (SO 2 C 2 F 5 ) 2 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiSO 3 CF 3 , LiI, LiCl, LiB (C 2 O 4 ) 2, etc. may be used alone or in combination.
• LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN (SO 2 F) 2 , LiN (SO 2 CF 3 ) 2, LiN (SO 2 C 2 F 5 ) 2 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiSO 3 CF 3 , LiI, LiCl, LiB (C 2 O 4 ) 2, etc. may be used alone or in
• the concentration (content) of the lithium salt in the electrolyte may be 0.9 M to 3.0 M (mol / liter), specifically 1.0 M to 2.0 M.
• the electrolyte additive according to the present invention is 0.05 to 20% by weight, 0.05 to 15% by weight, 0.05 to 10% by weight, 0.1 to 10% by weight, 0.1 to 8% by weight, 0.1 to the total weight of the electrolyte 6 wt%, 0.1-4 wt%, 0.1-3 wt%, 0.2-5 wt%, 0.5-15 wt%, 0.5-10 wt%, 0.5-8 wt%, 0.5-6 wt%, 0.5-4 wt% %, 0.5 to 3 wt%, 1 to 10 wt%, 1 to 8 wt%, 3 to 10 wt%, 3 to 8 wt%, 3 to 6 wt%, 4 to 10 wt%, 4 to 8 wt%, It may be included in an amount of 4 to 7% by weight or 5 to 7% by weight.
• the compound of Formula 1 is included in the content range, it is possible to further improve output characteristics by suppressing an increase in resistance, and
• the secondary battery electrolyte is other known additives (vinylene carbonate), fluoroethylene carbonate (fluoroethylene carbonate), succinonitrile (succinonitrile), adiponitrile (adiponitrile), vinyl ethylene carbonate (vinylethylene carbonate) ), Lithium difluorodioxalato phosphate, lithium tetrafluorooxalato phosphate, lithium difluorooxalato borate, and lithium difluorophosphate (lithium difluorodioxalato phosphate) lithium difluorophosphate, propene sultone, propane sultone, ethylene sulfate or ethylene sulfite may be included alone or in combination.
• the known additive may be added in a content range that does not affect the efficacy of the compound of Formula 1 and the performance of the electrolyte solution, for example, 0.1 wt% or more, for example, 0.1 to 10 wt% of the electrolyte solution, respectively. Can be added.
• the secondary battery electrolyte of the present invention may be prepared by mixing and stirring a non-aqueous solvent, a lithium salt and the secondary battery electrolyte additive, and at this time, a known electrolyte additive commonly used in the electrolyte may be further mixed.
• the present invention provides a secondary battery comprising the secondary battery electrolyte as described above.
• the secondary battery of the present invention can be any kind of secondary battery including the above-described secondary battery electrolyte.
• the secondary battery of the present invention includes a positive electrode including a positive electrode active material; A negative electrode including a negative electrode active material; A separator disposed between the anode and the cathode; And the above-described secondary battery electrolyte as a component.
• the positive electrode includes a positive electrode active material capable of reversibly adsorbing and detaching lithium ions, and the positive electrode active material includes at least one selected from the group consisting of cobalt, manganese, iron, aluminum, and nickel; Or lithium composite metal oxides.
• the metal compound used for the positive electrode active material may be variously selected and selected from the group consisting of K, Na, Ca, Sn, V, Ge, Ga, B, As, Zr, Cr, Sr, V and rare earth elements in addition to these metals. It may further comprise a component.
• the negative electrode includes a negative electrode active material capable of adsorbing and desorbing lithium ions, and the negative electrode active material includes crystalline or amorphous carbon; Carbon-based negative electrode active material (thermally decomposed carbon, coke, graphite) of the carbon composite; Burnt organic polymer compound; Carbon fiber; Tin oxide compounds; Lithium metal; Or lithium alloys.
• the amorphous carbon may include hard carbon, coke, mesocarbon microbead (MCMB) fired at 1,500 ° C. or lower, mesophase pitch-based carbon fiber (MPCF), or the like. Can be.
• Examples of the crystalline carbon include a graphite material, and specific examples thereof include natural graphite, artificial graphite, graphitized coke, graphitized MCMB, graphitized MPCF, and the like.
• silicon, titanium, zinc, bismuth, cadmium, antimony, lead, tin, gallium, or indium may be used as another element forming an alloy with lithium.
• the separation membrane is for preventing a short circuit between the positive electrode and the negative electrode, a polyolefin-based polymer membrane such as polypropylene, polyethylene, or a multilayer thereof; Microporous film; web; And nonwoven fabrics may be used.
• a polyolefin-based polymer membrane such as polypropylene, polyethylene, or a multilayer thereof; Microporous film; web; And nonwoven fabrics may be used.
• Bicycloglyoxalsulfate of formula 1 used in the following examples is a known compound (CAS No. 496-45-7), ATOMAX (China), CHEMOS (Germany), ABICHEM (Germany), PEWAX (China) You can buy products sold by companies such as).
• the compound of Formula 1 may be prepared according to a known synthesis method such as Preparation Example 1.
• a 1,000 mL three neck flask and condenser were mounted in a 60 ° C. oil bath.
• 70 g of 1,1,2,2-tetrachloroethane was added to the three neck flask and the temperature was stabilized.
• 320 g of sulfuric acid (60% fuming grade) was added to initiate a reaction.
• the reaction solution initially exhibited a clear to light brown viscosity, and a crystalline solid was formed after 4 hours from the start of the reaction.
• the oil bath was cooled to room temperature and stirred slowly for an additional 3 hours. It was then replaced with a cold water bath at 5-7 ° C. and stirred slowly for an additional 2 hours.
• the reaction was terminated in the absence of further production of crystalline solids.
• ethylene carbonate (EC), 589 g of ethyl methyl carbonate (EMC), and 380 g of diethyl carbonate (DEC) were mixed to prepare a mixed liquid.
• EC ethylene carbonate
• EMC ethyl methyl carbonate
• DEC diethyl carbonate
• 167.1 g of LiPF 6 was added to the mixed liquid, and 1.1 M of LiPF 6 was added.
• bicycloglyoxal sulfate of Chemical Formula 1 was added in an amount of 0.5% by weight as an additive to prepare an electrolyte solution for a secondary battery.
• An electrolyte solution was prepared in the same manner as in Example 1, except that bicycloglyoxal sulfate of Chemical Formula 1 was added in an amount of 1.5 wt%.
• An electrolyte solution was prepared in the same manner as in Example 1, except that bicycloglyoxal sulfate of Chemical Formula 1 was added in an amount of 3% by weight.
• An electrolyte solution was prepared in the same manner as in Example 1, except that bicycloglyoxal sulfate of Chemical Formula 1 was added in an amount of 10% by weight.
• An electrolyte solution was prepared in the same manner as in Example 1, except that bicycloglyoxal sulfate of Chemical Formula 1 was added in an amount of 15% by weight.
• An electrolyte solution was prepared in the same manner as in Example 1, except that bicycloglyoxal sulfate of Chemical Formula 1 was added in an amount of 0.01% by weight.
• An electrolyte solution was prepared in the same manner as in Example 1, except that bicycloglyoxal sulfate of Chemical Formula 1 was not added.
• An electrolyte solution was prepared in the same manner as in Example 1, except that 1,3-trimethylene sultone was added in an amount of 3% by weight instead of the bicycloglyoxalsulfate of Formula 1. .
• An electrolyte solution was prepared in the same manner as in Example 1, except that bis (carboxymethyl) disulfide was added in an amount of 3% by weight instead of bicycloglyoxalsulfate of Chemical Formula 1.
• An electrolyte was prepared in the same manner as in Example 1, except that ethylene sulfite was added in an amount of 3% by weight instead of bicycloglyoxalsulfate of Chemical Formula 1.
• a 1.3 Ah pouch battery was assembled in a conventional manner using a positive electrode mixed with LiNi 0.5 Co 0.2 Mn 0.3 and LiMnO 2 in a 1: 1 weight ratio and a negative electrode mixed with artificial graphite and natural graphite in a 1: 1 weight ratio. Then, 6 g of the electrolyte solution prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were injected to complete a secondary battery.
• the impedance obtained when the obtained secondary battery was discharged at 3C for 10 seconds while maintaining a 60% state of charge voltage compared to full charge at room temperature was measured (used equipment: PNE-0506 charger / discharger). After measuring the initial impedance at room temperature of the secondary battery in the above manner, it was stored in a 70 °C high temperature oven and after 1 week and 2 weeks, each discharge impedance was measured.
• Table 1 shows the comparison of the impedance of the battery using an electrolyte solution containing a bicycloglyoxal sulfate of Formula 1 or a non-containing electrolyte
• Table 2 shows an electrolyte solution containing the additive of Formula 1 or other additives of the same content The impedances of the batteries used are compared.
• Example 1 division Impedance (m ⁇ ) Room temperature (initial) 70 degrees Celsius (one week passage) 70 degrees Celsius (after two weeks)
• Example 1 32 39 46
• Example 2 34 36 39
• Example 3 38 39
• Example 4 41
• 40 42
• Example 5 42
• Example 6 34
• Comparative Example 1 34 55 80
• Table 3 shows a comparison of the life characteristics of the battery using an electrolyte solution containing a bicycloglyoxal sulfate of Formula 1 or a non-containing electrolyte
• Table 4 is an electrolyte solution containing the additive of Formula 1 or other additives of the same content It is shown by comparing the life characteristics of the battery using.
• Table 5 shows a comparison of the life characteristics of the battery using an electrolyte solution containing the bicycloglyoxal sulfate of Formula 1 or a non-containing electrolyte
• Table 6 is an electrolyte solution containing the additive of Formula 1 or other additives of the same content It is shown by comparing the life characteristics of the battery using.
• the electrolyte additive for a secondary battery of the present invention can be provided in the electrolyte to provide a secondary battery having excellent physical properties in terms of output characteristics, life characteristics, storage characteristics and withstand voltage characteristics, it can be used for mobile, electric vehicles, power tools, electric It can be usefully used for secondary batteries for bikes, robots or drones.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Inorganic Chemistry (AREA)
• Secondary Cells (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=57757479

Family Applications (1)

Country Status (3)

Cited By (13)

Families Citing this family (5)

Citations (5)

Family Cites Families (11)

• 2016
  • 2016-07-14 WO PCT/KR2016/007652 patent/WO2017010820A1/ko not_active Ceased
  • 2016-07-14 JP JP2017564835A patent/JP6735777B2/ja active Active
  • 2016-07-14 KR KR1020160089152A patent/KR102510110B1/ko active Active

Patent Citations (5)

Also Published As

Similar Documents

Legal Events