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WO2017030416A1 - Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant - Google Patents

Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant Download PDF

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Publication number
WO2017030416A1
WO2017030416A1 PCT/KR2016/009183 KR2016009183W WO2017030416A1 WO 2017030416 A1 WO2017030416 A1 WO 2017030416A1 KR 2016009183 W KR2016009183 W KR 2016009183W WO 2017030416 A1 WO2017030416 A1 WO 2017030416A1
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WIPO (PCT)
Prior art keywords
electrolyte
secondary battery
lithium secondary
group
formula
Prior art date
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Ceased
Application number
PCT/KR2016/009183
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English (en)
Korean (ko)
Inventor
안경호
이철행
정이진
이정훈
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LG Chem Ltd
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LG Chem Ltd
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.)
Filing date
Publication date
Priority claimed from KR1020160104607A external-priority patent/KR101997812B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2018509518A priority Critical patent/JP6541873B2/ja
Priority to US15/750,707 priority patent/US10693179B2/en
Priority to PL16837358T priority patent/PL3324478T3/pl
Priority to CN201680048474.0A priority patent/CN107925128B/zh
Priority to EP16837358.7A priority patent/EP3324478B1/fr
Publication of WO2017030416A1 publication Critical patent/WO2017030416A1/fr
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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a lithium secondary battery electrolyte and a lithium secondary battery comprising the same, which can ensure cycle life characteristics and high temperature durability.
  • a battery is a device that converts chemical energy generated during the electrochemical redox reaction of chemical substances into electrical energy.
  • a primary battery that needs to be discarded when all the energy inside the battery is consumed and a rechargeable battery that can be recharged many times Can be divided into:
  • the secondary battery has an advantage of being able to be charged and discharged many times using reversible mutual conversion of chemical energy and electrical energy.
  • the lithium secondary battery is rechargeable, and has an advantage that the energy density per unit weight is three times higher than that of a conventional lead storage battery, nickel-cadmium battery, nickel hydrogen battery, and nickel zinc battery, and enables fast charging. It is widely used as a driving power source for portable electronic devices such as video cameras, mobile phones, and notebook computers.
  • the lithium secondary battery includes a cathode including a cathode active material capable of intercalation and deintercalation of lithium, and a cathode including a cathode active material capable of intercalating and deintercalating lithium. It is used by injecting an electrolyte solution into a containing battery cell.
  • a non-aqueous organic solvent in which lithium salt is dissolved is used instead of an aqueous electrolyte having high reactivity with lithium.
  • the organic solvent is preferably stable at high voltage, has high ion conductivity, high dielectric constant, and low viscosity.
  • a passivation layer such as a solid electrolyte interface (hereinafter referred to as an 'SEI film') is formed on the surface of the cathode, and a protection layer is formed on the surface of the anode.
  • the SEI membrane and the protective layer prevent the decomposition of the electrolyte during charging and discharging and serve as an ion tunnel. Therefore, as the SEI film and the protective layer have high stability and low resistance, the lifespan of the lithium secondary battery may be improved.
  • the present invention provides a lithium secondary battery electrolyte comprising an electrolyte additive that can improve the battery performance.
  • the present invention provides a lithium secondary battery comprising the electrolyte solution for the lithium secondary battery.
  • An electrolyte solution for a lithium secondary battery containing an electrolyte salt and an organic solvent
  • the electrolyte provides a lithium secondary battery electrolyte further comprising a compound represented by the following formula (1) as an electrolyte additive.
  • R is a linear or branched alkylene group having 1 to 3 carbon atoms
  • R 1 is a linear or branched alkylene group having 1 to 5 carbon atoms or an arylene group having 5 to 8 carbon atoms,
  • n is an integer of 0-10.
  • the compound represented by Chemical Formula 1 may be included in an amount of 0.05 wt% to 7 wt% based on the total weight of the electrolyte.
  • a lithium secondary battery including an electrolyte solution for a lithium secondary battery of the present invention.
  • a lithium secondary battery can be manufactured.
  • Example 1 is a graph showing a result of maintaining a high temperature (60 ° C.) storage capacity of a lithium secondary battery according to Experimental Example 1 of the present invention.
  • Figure 2 is a graph showing the results of the change in the thickness of the cell at high temperature (60 °C) storage of the lithium secondary battery according to Experimental Example 1 of the present invention.
  • a and “b” means the number of carbon atoms in the specific functional group. That is, the functional group may include “a” to "b” carbon atoms.
  • “carbon atoms, linear or branched alkylene group of 1 to 3” is an alkyl group containing carbon atoms of 1 to 3 carbon atoms, i.e. -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH (CH 3 )-, and -CH (CH 3 ) CH 2- .
  • alkyl group or "alkylene group” means a branched or unbranched aliphatic hydrocarbon group.
  • the alkyl group or alkylene group may be substituted or unsubstituted.
  • aryl group or "arylene group” herein means an aromatic ring or aromatic ring system (i.e., a ring sharing adjacent atom pairs) containing only carbon in the ring backbone. When aryl is a ring system, all rings in the system are aromatic.
  • the arylene group is a phenylene group, biphenylene group, naphthylene group, phenanthrenylene group, naphthacenylene group and the like, but is not limited thereto. In other embodiments, aryl groups may be substituted or unsubstituted.
  • Lithium secondary batteries known to date are difficult to prevent corrosion of metal materials, and in particular, there are insufficient points in maintaining performance at effective levels under extreme conditions such as overcharge, overdischarge, and high temperature storage. Accordingly, the present invention provides a lithium secondary battery electrolyte comprising an additive capable of preventing chemical reaction between the electrolyte and the electrode by forming an SEI film and a protective layer on the electrode surface, respectively, to improve the life characteristics and high temperature safety lithium secondary The battery can be manufactured.
  • An electrolyte solution for a lithium secondary battery containing an electrolyte salt and an organic solvent
  • the electrolyte provides a lithium secondary battery electrolyte further comprising a compound represented by the following formula (1) as an electrolyte additive.
  • R is a linear or branched alkylene group having 1 to 3 carbon atoms
  • R 1 is a linear or branched alkylene group having 1 to 5 carbon atoms or an arylene group having 5 to 8 carbon atoms,
  • n is an integer of 0-10.
  • R is a linear alkylene group having 1 to 3 carbon atoms
  • R 1 is an arylene group having 5 to 8 carbon atoms
  • n is an integer of 0 to 5.
  • the electrolyte solution of the present invention when the electrolyte solution contains a compound containing a sulfonate group as a substituent, such as the compound represented by the formula (1), by the coordination bond between the sulfonate group and the electrode current collector metal on the electrode surface A stable film can be formed to prevent corrosion of the electrode, particularly the anode surface. That is, when the electrode surface of the lithium secondary battery is exposed to the electrolyte under extreme conditions such as overcharge, overdischarge, and high temperature storage, it reacts with the sulfonate group and the hydroxyl group of the electrode surface of the compound included in the electrolyte additive as shown in Scheme 1 below. While water molecules are detached and oxygen of the sulfonate group forms coordination bonds with sites having a positive charge on the surface of the metal component of the electrode current collector, a film is formed on the surface of the electrode. The chemical reaction of the electrode can be suppressed.
  • a compound containing a sulfonate group as a substituent such
  • the compound containing an unsaturated functional group such as a triple bond or a polar functional group at the terminal since it accepts electrons more easily from the negative electrode than the polar solvent, it is reduced at a voltage lower than that of the polar solvent and thus polarized.
  • the solvent may be reduced before it is reduced. That is, the unsaturated or polar functional groups contained in the compound represented by Formula 1 may be more easily reduced and / or decomposed into radicals and / or ions upon charging.
  • radicals and / or ions may precipitate or form insoluble compounds by bonding with lithium ions, and the insoluble compounds react with various functional groups present on the surface of the carbon-based negative electrode or the carbon-based negative electrode itself to form covalent bonds. Or adsorbed on the cathode surface.
  • a modified SEI film having improved stability capable of maintaining a solid state even after prolonged charging and discharging is formed on the cathode surface.
  • Such a rigid modified SEI membrane can effectively reduce or prevent the penetration of the electrolyte can reduce the gas generated during high temperature storage.
  • a compound containing an isocyanate group or a nitrile group as a substituent such as the compound represented by Chemical Formula 1
  • the electrolyte additive of the present invention includes a compound containing the isocyanate group or the nitrile group as a substituent
  • the complex is formed on the electrode surface by reacting with various transition metal ions or hydroxyl groups present on the electrode surface as shown in Scheme 2 below. It can form a modified protective film consisting of a complex (complex).
  • the coating formed by such a composite can ensure stability by maintaining a solid state for a long time even after high temperature, charging and discharging, compared to the coating (protective layer) formed only by decomposition of the organic solvent.
  • This robust modified protective layer can more effectively block the entry of the organic solvent solvated by the lithium ions into the electrode during the intercalation of the lithium ions. Therefore, since the modified protective film more effectively blocks direct contact between the organic solvent and the positive electrode, reversibility of lithium ion occlusion / release can be further improved, and consequently, a high temperature stability improvement effect of the battery can be realized.
  • the compound represented by the formula (1) containing a triple bond structure, both a sulfonate group and an isocyanate group (-NCO) in the compound as an electrolyte additive, the positive and negative electrode surface By forming stable SEI films and protective films on the substrates, high temperature life characteristics and high temperature durability of the lithium secondary battery can be remarkably improved even under extreme conditions such as high temperature storage.
  • the compound represented by Formula 1 may be represented by the following Formula 1a or 1b.
  • the compound represented by Formula 1 may be included in 0.05 wt% to 7 wt%, preferably 0.1 wt% to 5 wt% based on the total weight of the electrolyte. If the additive is contained in less than 0.05% by weight, since the effect of forming the SEI film and the protective film on the electrode surface is inadequate, the capacity deteriorates with a longer storage period, and when the additive content exceeds 7% by weight, such as side reactions. Since the gas generation suppression effect is insufficient due to the generation, it may cause a problem that the battery thickness increases with the interpolation period.
  • the electrolyte salt is (i) Li +, Na + and K + cations and (ii) selected from the group consisting of PF 6 -, BF 4 -, Cl -, Br -, I - , ClO 4 -, AsF 6 - , B 10 Cl 10 -, CH 3 CO 2 -, CF 3 SO 3 -, CF 3 SO 3 -, SbF 6 -, AlCl 4 -, AlO 4 -, CH 3 SO 3 - , N (CF 3 SO 2) 2 - and C (CF 2 SO 2) 3 - can be made of a combination of an anion selected from the group, typically, examples of LiCl, LiBr, LiI, LiClO 4, LiBF 4, LiB 10 consisting of Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiAlCl 4
  • the electrolyte salt may include a single substance or a mixture of two or more selected from the group consisting of LiPF 6 , LiCH 3 CO 2 , LiCF 3 CO 2 , LiCH 3 SO 3 , LiFSI, LiTFSI, and (CF 3 SO 2 ) 2 NLi. have.
  • the electrolyte salt may be appropriately changed within a usable range, but may be included in an electrolyte solution at a concentration of 0.8 M to 1.5 M in order to obtain an effect of forming an anti-corrosion coating on the surface of an electrode. If the concentration of the electrolyte salt exceeds 1.5M, it is difficult to realize a stable film forming effect.
  • the non-aqueous organic solvent may include conventional organic solvents usable as non-aqueous organic solvents of lithium secondary batteries, such as cyclic carbonate solvent, linear carbonate solvent, ester solvent or ketone solvent. These may be used alone or in combination of two or more in an appropriate ratio.
  • the cyclic carbonate solvent may include one or two or more mixed solutions selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC) and butylene carbonate (BC).
  • the linear carbonate solvent is dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), ethyl methyl carbonate (EMC), vinylene carbonate (VC), fluoroethylene carbonate (FEC), methyl 1 type, or 2 or more types of mixed solution chosen from the group which consists of propyl carbonate (MPC) and ethylpropyl carbonate (EPC).
  • ester solvent is methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -valerolactone and ⁇ -1 type, or 2 or more types of mixed solution chosen from the group which consists of caprolactone is mentioned.
  • polymethylvinyl ketone or the like may be used as the ketone solvent.
  • the present invention provides a lithium secondary battery including the positive electrode, the negative electrode, a separator interposed between the positive electrode and the negative electrode, and an electrolyte solution, the lithium secondary battery comprising the electrolyte solution for the lithium secondary battery of the present invention as the electrolyte solution.
  • the positive electrode may be formed by coating a positive electrode active material on an electrode current collector, wherein the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical change in the battery, for example, stainless steel, Aluminum, nickel, titanium, calcined carbon, or a surface treated with carbon, nickel, titanium, silver, or the like on the surface of aluminum or stainless steel may be used.
  • the positive electrode current collector may use various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric having fine irregularities formed on a surface thereof so as to increase the adhesion with the positive electrode active material.
  • the positive electrode active material is not particularly limited as long as it is a lithium-containing transition metal oxide used as a positive electrode active material in the manufacture of a general lithium secondary battery.
  • the negative electrode may be formed by coating a negative electrode active material on a negative electrode current collector, and the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes in the battery.
  • copper and stainless steel Aluminum, nickel, titanium, calcined carbon, surface treated with carbon, nickel, titanium, silver, and the like on the surface of copper or stainless steel, aluminum-cadmium alloy and the like can be used.
  • the negative electrode current collector like the positive electrode current collector, may be used in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric having fine irregularities formed on a surface thereof.
  • the negative electrode active material may be a carbon material, lithium metal, silicon or tin that can be stored and released lithium ions in the manufacturing of a general lithium secondary battery, for example, low crystalline carbon and high crystallinity Both carbon and the like can be used.
  • Soft crystalline carbon and hard carbon are typical low crystalline carbon
  • high crystalline carbon is natural graphite, Kish graphite, pyrolytic carbon, liquid crystal pitch-based carbon fiber.
  • high temperature calcined carbon such as mesophase pitch based carbonfiber, meso-carbon microbeads, mesophase pitches and petroleum or coal tar pitch derived cokes.
  • the positive electrode and the negative electrode active material may further include a binder and a conductive material.
  • the binder is a component that assists the bonding between the conductive material, the active material and the current collector, and is typically added in an amount of 1 to 50 wt% based on the total weight of the electrode mixture.
  • binders include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoro Low ethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, various copolymers thereof, and the like.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene polymer
  • sulfonated-EPDM styrene-butadiene rubber
  • fluorine rubber various
  • the conductive material is a component for further improving the conductivity of the electrode active material, and may be added in an amount of 1 to 20 wt% based on the total weight of the electrode mixture.
  • a conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery, and examples thereof include graphite such as natural graphite and artificial graphite; Carbon blacks such as acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride powder, aluminum powder and nickel powder; Conductive whiskeys such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Conductive materials such as polyphenylene derivatives and the like can be used.
  • the electrolyte solution containing the additive for preventing corrosion of the electrode of the present invention is impregnated with an electrolyte solution
  • the battery The formation process can be performed.
  • the urethane reaction efficiency between -NCO, which is the terminal group of the compound represented by Formula 1, and OH, which is an impurity on the electrode surface is further increased, and thus the protective effect is more enhanced. I think it will increase.
  • a passivation film is formed on the electrode surface to prevent the electrode surface from being exposed even under extreme conditions such as overcharge, overdischarge, and high temperature storage, thereby preventing electrode corrosion.
  • Various performances, such as the cycle life characteristic of a secondary battery, can be improved.
  • a negative electrode active material slurry was prepared. The slurry was applied on a 10 ⁇ m thick copper current collector using a doctor blade to a thickness of about 60 ⁇ m, dried for 0.5 hours in a hot air dryer at 100 ° C., and then dried again under vacuum, 120 ° C. for 4 hours, and rolled. (roll press) to prepare a negative electrode plate.
  • SBR styrene-butadiene rubber
  • CMC carboxymethylcellulose
  • FCG6 artificial graphite
  • the slurry was applied on a 20 ⁇ m thick aluminum current collector using a doctor blade, dried about 0.5 ⁇ m in a hot air dryer at 100 ° C., and then dried again under vacuum, 120 ° C. for 4 hours, and rolled. (roll press) to prepare a positive electrode plate.
  • An electrode assembly is manufactured through a separator of porous polyethylene having a thickness of 14 ⁇ m coated with a ceramic between the negative electrode prepared above and the negative electrode, the electrode assembly is placed in a case, and the prepared electrolyte is transferred into the case. Injected to prepare a lithium secondary battery.
  • An electrolyte and a lithium secondary battery including the same were prepared in the same manner as in Example 1, except that 3 wt% of the compound of Formula 1b was used instead of the compound of Formula 1a as an electrolyte additive.
  • An electrolyte solution and a lithium secondary battery including the same were prepared in the same manner as in Example 1, except that 0.02% by weight of the compound of Formula 1a was included as an electrolyte additive.
  • An electrolyte solution and a lithium secondary battery were manufactured in the same manner as in Example 1, except that 7.3 wt% of the compound of Formula 1a was included as an electrolyte additive.
  • the secondary batteries of Examples 1 and 2 have a lower capacity decay reduction rate according to storage periods than the secondary batteries of Comparative Examples 1 to 3.
  • the secondary batteries of Examples 1 and 2 have a lower cell thickness increase (change) according to the storage period compared to those of Comparative Examples 1 to 3.

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Abstract

La présente invention concerne un électrolyte pour batterie secondaire au lithium, comprenant un additif pour la formation d'un film SEI stable et une couche de protection sur la surface d'une électrode pour empêcher une réaction chimique entre l'électrolyte et l'électrode, et une batterie secondaire au lithium comprenant l'électrolyte, qui présente des propriétés de durée de vie et de sécurité à haute température améliorées.
PCT/KR2016/009183 2015-08-19 2016-08-19 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant Ceased WO2017030416A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2018509518A JP6541873B2 (ja) 2015-08-19 2016-08-19 リチウム二次電池用電解液およびこれを含むリチウム二次電池
US15/750,707 US10693179B2 (en) 2015-08-19 2016-08-19 Electrolyte solution for lithium secondary battery and lithium secondary battery comprising the same
PL16837358T PL3324478T3 (pl) 2015-08-19 2016-08-19 Elektrolit dla akumulatora litowego i zawierający go akumulator litowy
CN201680048474.0A CN107925128B (zh) 2015-08-19 2016-08-19 用于锂二次电池的电解质溶液和包括该电解质溶液的锂二次电池
EP16837358.7A EP3324478B1 (fr) 2015-08-19 2016-08-19 Électrolyte pour batterie secondaire au lithium et batterie secondaire au lithium la comprenant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20150116637 2015-08-19
KR10-2015-0116637 2015-08-19
KR1020160104607A KR101997812B1 (ko) 2015-08-19 2016-08-18 리튬 이차전지용 전해액 및 이를 포함하는 리튬 이차전지
KR10-2016-0104607 2016-08-18

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Cited By (3)

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CN109904457A (zh) * 2019-03-26 2019-06-18 湖州昆仑动力电池材料有限公司 一种锂离子电池电解液用阻燃添加剂及应用
WO2019114685A1 (fr) * 2017-12-15 2019-06-20 华为技术有限公司 Additif électrolytique, électrolyte de batterie secondaire au lithium et batterie secondaire au lithium
CN114583277A (zh) * 2020-03-27 2022-06-03 宁德新能源科技有限公司 电化学装置及包括其的电子装置

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019114685A1 (fr) * 2017-12-15 2019-06-20 华为技术有限公司 Additif électrolytique, électrolyte de batterie secondaire au lithium et batterie secondaire au lithium
CN109935904A (zh) * 2017-12-15 2019-06-25 华为技术有限公司 一种电解液添加剂、锂二次电池电解液和锂二次电池
US20200303775A1 (en) * 2017-12-15 2020-09-24 Huawei Technologies Co., Ltd. Electrolyte Additive, Lithium Secondary Battery Electrolyte, and Lithium Secondary Battery
EP3719912A4 (fr) * 2017-12-15 2021-01-27 Huawei Technologies Co., Ltd. Additif électrolytique, électrolyte de batterie secondaire au lithium et batterie secondaire au lithium
CN109935904B (zh) * 2017-12-15 2021-08-20 华为技术有限公司 一种电解液添加剂、锂二次电池电解液和锂二次电池
CN109904457A (zh) * 2019-03-26 2019-06-18 湖州昆仑动力电池材料有限公司 一种锂离子电池电解液用阻燃添加剂及应用
CN109904457B (zh) * 2019-03-26 2022-05-13 湖州昆仑亿恩科电池材料有限公司 一种锂离子电池电解液用阻燃添加剂及应用
CN114583277A (zh) * 2020-03-27 2022-06-03 宁德新能源科技有限公司 电化学装置及包括其的电子装置

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