WO2017057963A1 - Électrolyte non aqueux et pile rechargeable au lithium le comprenant - Google Patents

Électrolyte non aqueux et pile rechargeable au lithium le comprenant Download PDF

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Publication number
WO2017057963A1
WO2017057963A1 PCT/KR2016/011000 KR2016011000W WO2017057963A1 WO 2017057963 A1 WO2017057963 A1 WO 2017057963A1 KR 2016011000 W KR2016011000 W KR 2016011000W WO 2017057963 A1 WO2017057963 A1 WO 2017057963A1
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WO
WIPO (PCT)
Prior art keywords
lithium
aqueous electrolyte
weight
carbonate
secondary battery
Prior art date
Application number
PCT/KR2016/011000
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English (en)
Korean (ko)
Inventor
김하은
임영민
이철행
김광연
이용범
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from KR1020160125916A external-priority patent/KR102034810B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Publication of WO2017057963A1 publication Critical patent/WO2017057963A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

  • a carbon-based negative electrode active material such as crystalline carbon, amorphous carbon, or a carbon composite may be used alone or in combination of two or more thereof.
  • the crystalline carbon is graphite such as natural graphite and artificial graphite. (graphite) carbon.
  • 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 about 10 ⁇ m, dried to prepare a negative electrode, and then roll-rolled to prepare a negative electrode.
  • Cu copper
  • the positive electrode and the negative electrode prepared as described above were manufactured with a polymer battery by a conventional method with a separator composed of three layers of polypropylene / polyethylene / polypropylene (PP / PE / PP), followed by pouring the prepared non-aqueous electrolyte solution into a lithium secondary battery. The manufacture of the battery was completed.
  • LiPF 6 A non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that the amounts were changed to 0.14 mol / L and 0.86 mol / L of lithium bisfluorosulfonylimide (about 1: 6 molar ratio). Was prepared.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1, except that 2,3-difluorobiphenyl was used at 3% by weight.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2, except that 10% by weight of 2,3-difluorobiphenyl was used.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2 except that the 2,3-difluorobiphenyl was used at 0.5 wt%.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 2 except that 2-fluorobiphenyl was used instead of 2,3-difluorobiphenyl.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC ethylmethyl carbonate
  • a nonaqueous electrolyte solution and a lithium secondary battery were prepared.
  • EC ethylene carbonate
  • DMC ethylmethyl carbonate
  • PC propylene carbonate
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that LiFSI and 2,3-difluorobiphenyl were not used.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that LiFSI was not used.
  • a non-aqueous electrolyte solution and a lithium secondary battery were prepared in the same manner as in Example 1 except that 2,3-difluorobiphenyl was not used.
  • the low-temperature output is calculated from the voltage difference generated by discharging the lithium secondary batteries of Examples 1 to 9 and Comparative Examples 1 to 5 from SOC (charge depth) of 50 to 5 C at room temperature for 10 seconds. It was. Subsequently, after storing the lithium secondary batteries of Examples 1 to 9 and Comparative Examples 1 to 5 for 16 weeks at 60 ° C., the battery was discharged at 50 ° C. at 50% of SOC (charge depth) for 10 seconds at low temperature. The output was calculated, and the output was taken after 16 weeks.
  • LiPF 6 LiFSI Additive (% by weight) High Temperature Storage Characteristics (%) Life characteristic (%) Volume Print Battery thickness increase Room temperature High temperature
  • Example 1 9 DFBP 5 89.3 91.2 9.8 86.9 87.4
  • Example 2 1: 6 DFBP 5 89 91.4 10.3 85.7 86.8
  • Example 3 1: 5 DFBP 5 87.1 90.6 11 86.1 84.6
  • Example 4 1: 9 DFBP 3 90.9 92.5 8.6 90.9 88.2
  • Example 5 1: 6 DFBP 3 90.4 91.8 8.3 90.4 87.4
  • Example 6 6 DFBP 10 84.3 90.7 14.9 82.6 80.7
  • Example 7 1: 6 DFBP 0.5 86.7 87.6 13.8 85 83.1
  • Comparative Example 1 9 DFBP 5 81.6 84.9 19.1 45.1
  • 2,3-di 2,3-difluorobiphenyl is contained in the case of Examples 1 to 5 containing 3 to 5% by weight relative to the total weight of the non-aqueous electrolyte It showed an excellent effect compared to Example 6 containing 10% by weight of fluorobiphenyl and Example 7 containing 0.5% by weight of 2,3-difluorobiphenyl.
  • the lithium secondary batteries of Example 1 and Comparative Example 5 were overcharged to 8.3 V under constant current / constant voltage (CC / CV) conditions at 1 C (775 mAh) / 12 V from a layered state at 25 ° C., and the temperature of the battery at that time And the voltage change is measured and shown in FIG.
  • CC / CV constant current / constant voltage

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

Abstract

La présente invention concerne un électrolyte non aqueux et une pile rechargeable au lithium le comprenant, l'électrolyte non aqueux comprenant : i) un solvant organique non aqueux contenant du carbonate de propylène (PC) et du carbonate d'éthylène (EC) ; ii) du bis(fluorosulfonyl)imide de lithium (LiFSI) ; et iii) un composé biphényle fluoré. L'électrolyte non aqueux selon la présente invention peut améliorer les caractéristiques de sortie à basse température et à température ambiante par formation d'une forte membrane SEI dans une cathode pendant la charge initiale de la pile rechargeable au lithium comprenant l'électrolyte non aqueux, et peut améliorer les caractéristiques de cycle à haute température et à température ambiante et les caractéristiques de capacité après stockage à haute température.
PCT/KR2016/011000 2015-09-30 2016-09-30 Électrolyte non aqueux et pile rechargeable au lithium le comprenant WO2017057963A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0138026 2015-09-30
KR20150138026 2015-09-30
KR1020160125916A KR102034810B1 (ko) 2015-09-30 2016-09-29 비수성 전해액 및 이를 포함하는 리튬 이차전지
KR10-2016-0125916 2016-09-29

Publications (1)

Publication Number Publication Date
WO2017057963A1 true WO2017057963A1 (fr) 2017-04-06

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116053590A (zh) * 2023-03-28 2023-05-02 广汽埃安新能源汽车股份有限公司 一种锂离子电池电解液、锂离子电池以及用电设备
EP4246640A1 (fr) * 2022-03-18 2023-09-20 Toyota Jidosha Kabushiki Kaisha Matériau conducteur d'ions lithium et batterie secondaire au lithium

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003203673A (ja) * 2001-12-28 2003-07-18 Mitsui Chemicals Inc 非水電解液およびそれを含むリチウム二次電池
US20050042521A1 (en) * 1998-09-03 2005-02-24 Toshikazu Hamamoto Non-aqueous secondary battery having increased discharge capacity retention
KR20120090969A (ko) * 2009-09-29 2012-08-17 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 전지 및 비수계 전해액
KR20140093976A (ko) * 2011-02-10 2014-07-29 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 용액 및 그것을 적용한 비수계 전해액 이차 전지
KR20150034499A (ko) * 2013-09-26 2015-04-03 주식회사 엘지화학 출력 성능이 개선된 리튬이차전지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050042521A1 (en) * 1998-09-03 2005-02-24 Toshikazu Hamamoto Non-aqueous secondary battery having increased discharge capacity retention
JP2003203673A (ja) * 2001-12-28 2003-07-18 Mitsui Chemicals Inc 非水電解液およびそれを含むリチウム二次電池
KR20120090969A (ko) * 2009-09-29 2012-08-17 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 전지 및 비수계 전해액
KR20140093976A (ko) * 2011-02-10 2014-07-29 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 용액 및 그것을 적용한 비수계 전해액 이차 전지
KR20150034499A (ko) * 2013-09-26 2015-04-03 주식회사 엘지화학 출력 성능이 개선된 리튬이차전지

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4246640A1 (fr) * 2022-03-18 2023-09-20 Toyota Jidosha Kabushiki Kaisha Matériau conducteur d'ions lithium et batterie secondaire au lithium
CN116053590A (zh) * 2023-03-28 2023-05-02 广汽埃安新能源汽车股份有限公司 一种锂离子电池电解液、锂离子电池以及用电设备

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