WO2020135584A1 - Additif de formation de film d'électrode positive pour électrolyte de batterie, et électrolyte et batterie au lithium utilisant l'additif - Google Patents

Additif de formation de film d'électrode positive pour électrolyte de batterie, et électrolyte et batterie au lithium utilisant l'additif Download PDF

Info

Publication number
WO2020135584A1
WO2020135584A1 PCT/CN2019/128699 CN2019128699W WO2020135584A1 WO 2020135584 A1 WO2020135584 A1 WO 2020135584A1 CN 2019128699 W CN2019128699 W CN 2019128699W WO 2020135584 A1 WO2020135584 A1 WO 2020135584A1
Authority
WO
WIPO (PCT)
Prior art keywords
electrolyte
additive
lithium ion
ion battery
battery
Prior art date
Application number
PCT/CN2019/128699
Other languages
English (en)
Chinese (zh)
Inventor
马国强
张海兵
蒋志敏
沈旻
董经博
刘海岛
陈慧闯
李南
Original Assignee
浙江省化工研究院有限公司
中化蓝天集团有限公司
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
Application filed by 浙江省化工研究院有限公司, 中化蓝天集团有限公司 filed Critical 浙江省化工研究院有限公司
Publication of WO2020135584A1 publication Critical patent/WO2020135584A1/fr

Links

Images

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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/15—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same unsaturated acyclic carbon skeleton
    • 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
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0088—Composites
    • H01M2300/0091—Composites in the form of mixtures
    • 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 invention belongs to the field of lithium-ion battery electrolytes, and relates to an additive for a lithium-ion battery electrolyte, an electrolyte using the additive and a lithium-ion battery.
  • Lithium-ion batteries have the advantages of high energy density, long cycle life, high operating voltage, small self-discharge, and no memory effect. They are widely used in 3C, energy storage, and power batteries. Longer cycle life, higher energy density, faster rate performance, wider use temperature and lower price and cost are important directions for the development of lithium ion batteries.
  • Increasing the battery energy density can be achieved by increasing the battery charging cut-off voltage, for example: increasing the operating voltage of existing battery systems, such as LiCoO 2 and NMC ternary battery systems, the battery specific capacity increases by nearly 8% for each 0.1V increase in charging voltage. And its energy density increased by nearly 10%; the development of new battery systems.
  • Cathode materials such as LiCoPO 4 (4.8V), LiNi 0.5 Mn 1.5 O 4 (4.7V), Li 2 CoPO 4 F (5.1V), and LiNiPO 4 (5.1V) can be stably cycled at high voltage.
  • the electrolyte is easily oxidized and decomposed on the surface of the positive electrode at high voltage, resulting in high interface resistance and Battery capacity decay; the dissolution of metal cations in the electrolyte at high voltage will cause the destruction of the positive electrode structure and affect the battery cycle stability; the metal cations dissolved in the electrolyte will precipitate as metal dendrites in the graphite anode, affecting the battery safety . Therefore, suppressing the side reaction at the positive electrode/electrolyte interface at high voltage is a key measure to improve the performance of high-voltage lithium-ion batteries.
  • Positive electrode protection such as coating the surface of the positive electrode with some inorganic compounds (AlPO 4 , TiO 2 , AlF 3, etc.) to suppress the dissolution of metal elements in the positive electrode material and the oxidation of the electrolyte under high voltage, but the general resistance of the coating layer is relatively High, causing increased battery polarization and reduced rate performance.
  • Use electrolyte additives that is, use suitable electrolyte additives to form a good interface film on the positive electrode. At present, there is no electrolyte additive particularly suitable for forming a good interface film on the positive electrode.
  • the object of the present invention is to provide a battery electrolyte additive, which has the following structural formula (I):
  • R1 and R2 are independently selected from C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, C6-C20 aryl, C6-C20 haloaryl.
  • the substituents R1 and R2 are independently selected from C1-C20 alkyl, C2-C20 alkenyl, C1-C20 haloalkyl, C2-C20 haloalkenyl, C6 -C20 aryl, C6-C20 halogenated aryl.
  • the substituents R1, R2 are independently selected from C1-C12 alkyl, C2-C12 alkenyl, C1-C12 haloalkyl, C2-C12 haloalkenyl, C6-C12 aryl, C6-C12 Halogenated aryl.
  • substituents R1, R2 are independently selected from C1-C6 alkyl, C2-C6 alkenyl, C1-C6 haloalkyl, C2-C6 haloalkenyl.
  • the substituents R1, R2 are independently selected from C1-C3 alkyl, C2-C3 alkenyl, C1-C3 haloalkyl, C2-C3 haloalkenyl.
  • the battery electrolyte additive represented by the structural formula (I) provided by the present invention is suitable for use as a positive electrode film-forming additive in the battery electrolyte.
  • the positive electrode of the battery is preferably LiNi 0.5 Co 0.2 Mn 0.3 O 2 , lithium cobaltate, LiNi 0.5 Mn 1.5 O 4 or Li 1.13 [ Ni 0.2 Co 0.2 Mn 0.47 ]O 2 .
  • the present invention also provides a lithium ion battery electrolyte containing the compound represented by the above structural formula (I).
  • the content of the compound represented by structural formula (I) in the lithium ion battery electrolyte is preferably 0.02% to 2%. It is further preferred that the content of the compound represented by structural formula (I) in the electrolyte of the lithium ion battery is 0.1% to 1%.
  • the lithium ion battery electrolyte provided by the present invention may further contain a lithium salt, an organic solvent and additives in addition to the compound represented by the above structural formula (I), that is, the lithium ion battery electrolyte contains a lithium salt and an organic solvent , Additives and compounds represented by structural formula (I).
  • the lithium salt used may be a lithium salt commonly used in the art.
  • the lithium salt is selected from LiBF 4 , LiPF 6 , LiFSI, LiTFSI, LiAsF 6 , LiClO 4 , LiSO 3 CF 3 , LiC 2 O 4 BC 2 O 4 , LiF 2 BC 2 O 4 , LiDTI, LiPO 2 At least one of F 2 .
  • the lithium ion battery electrolyte provided by the present invention may use an organic solvent commonly used in the art.
  • the organic solvent is selected from at least one of carbonate, phosphate, carboxylate, ether, nitrile, and sulfone solvents.
  • the additive for the lithium ion battery electrolyte provided by the present invention may be an additive that helps improve the performance of the electrolyte.
  • the additive is selected from at least one of negative electrode film-forming additives, water-removing additives, positive electrode film-forming additives, conductivity-increasing additives, wettability-improving additives, and flame retardant additives.
  • the additive is selected from biphenyl, vinylene carbonate (VC), fluoroethylene carbonate, ethylene ethylene carbonate, propylene sulfite, butylene sulfite, 1,3-propanesulfonate Acid lactone (PS), 1,4-butane sultone, 1,3-(1-propene) sultone, vinyl sulfite, vinyl sulfate, cyclohexylbenzene, tris(trimethylsilane) boron
  • TMSB acid ester
  • TMSB tris(trimethylsilane) phosphate
  • tert-butylbenzene succinonitrile
  • succinic anhydride At least one of acid ester (TMSB), tris(trimethylsilane) phosphate, tert-butylbenzene, succinonitrile, ethylene glycol bis(propionitrile) ether, and succinic anhydride.
  • the additive is selected from the compound represented by structural formula (I) and selected from vinylene carbonate, 1,3-propane sultone, tris(trimethylsilane) borate, fluoro At least one of ethylene carbonate and ethylene ethylene carbonate.
  • the additive is selected from the compound represented by the structural formula (I) and at least one selected from the group consisting of vinylene carbonate, 1,3-propane sultone, and tris(trimethylsilane) borate. Species.
  • the lithium ion battery electrolyte according to the present invention contains a lithium salt, an organic solvent, an additive, and a compound represented by structural formula (I), the lithium salt, an organic solvent, an additive, and the compound represented by structural formula (I) are in the electrolyte
  • the content should improve battery performance.
  • the lithium salt content is 5 to 15%
  • the organic solvent content is 72 to 95%
  • the additive content is 0.2 to 10%
  • the content of the compound represented by structural formula (I) is 0.1% ⁇ 5%.
  • the invention also provides a lithium ion battery containing the above electrolyte.
  • the lithium ion battery according to the present invention also contains other commonly used components of the lithium ion battery described in the art.
  • the compound represented by the structural formula (I) provided by the present invention has the following advantages over the prior art when it is used in a battery electrolyte:
  • the present invention proposes a new positive electrode film-forming additive.
  • This positive electrode film-forming additive oxidizes and decomposes before the solvent, and the decomposition products are deposited on the surface of the positive electrode materials such as lithium cobalt oxide, nickel cobalt manganese, nickel manganese, and lithium-rich manganese. Can effectively improve the performance of the battery.
  • Figure 1 shows the LSV curves of the electrolytes prepared in Example 1 and Comparative Example 1.
  • FIG. 2 is an AC impedance spectrum after two cycles of assembling NCM523/metal lithium half-cells assembled from the electrolyte solutions prepared in Example 1 and Comparative Example 1, respectively.
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , conductive carbon black Super-P and binder polyvinylidene fluoride (PVDF) in a mass ratio of 93:4:3, and then mix them Dispersed in N-methyl-2-pyrrolidone (NMP) to obtain a positive electrode slurry.
  • NMP N-methyl-2-pyrrolidone
  • the slurry is evenly coated on both sides of the aluminum foil, after drying, rolling and vacuum drying, and the aluminum lead wire is welded with an ultrasonic welding machine to obtain a positive electrode plate.
  • a polyethylene microporous film with a thickness of 20 ⁇ m is placed between the positive electrode plate and the negative electrode plate as a separator, and then the sandwich structure composed of the positive electrode plate, the negative electrode plate and the separator is wound, and the electrode lugs are drawn out and encapsulated in an aluminum plastic film. Cell to be filled.
  • the electrolyte prepared above is injected into the battery cell, and the amount of the electrolyte should ensure that the voids in the battery cell are filled. Then proceed to the following steps: 0.01C constant current charging for 30min, 0.02C constant current charging for 60min, 0.05C constant current charging for 90min, 0.1C constant current charging for 240min, and then set aside for 1hr after shaping and sealing, and then further with 0.2C current constant
  • the battery is charged to 4.40V, and after being left at room temperature for 24hr, it is discharged to 3.0V with a constant current of 0.2C.
  • the capacity retention rate is calculated according to the following formula:
  • Capacity retention rate 300-week discharge capacity / 1st week discharge capacity * 100%.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 was replaced with a lithium-rich manganese-based positive electrode material Li 1.13 [Ni 0.2 Co 0.2 Mn 0.47 ]O 2 , the others are the same as in Example 1, and the data of the normal temperature cycle performance obtained by the test are Table 1.
  • the electrolytic solution prepared in Example 1 has an oxidative decomposition starting potential of about 4.80V and a decomposition peak of 5.2V. This shows that Compound 1 starts oxidative decomposition at 4.80V and forms on the surface of the positive electrode material. Stable interface film, this interface film can significantly passivate the side reaction between the electrode and the electrolyte. It can also be seen from Figure 1 that after Compound 1 is oxidized, the oxidation current of the electrolyte is very low, and no obvious oxidation decomposition current is observed until 6.7V, which shows that the CEI film formed on the surface of the positive electrode is more stable. It has better oxidation resistance.
  • Example 1 The electrolytes prepared in Example 1 and Comparative Example 1 were respectively assembled into NCM523/metal lithium half-cells, and the AC impedance spectra of the two NCM523/metal lithium half-cells after 2 weeks of circulation were tested. The test results are shown in FIG. 2 Show.
  • the NCM523/metal lithium half-cell assembled using the electrolyte prepared in Example 1 has a lower CEI film resistance after cycling, which shows that the additive shown in the structural formula (I) provided by the present invention can be significant Reduce the CEI membrane impedance of the battery under high voltage, thereby improving the battery's high voltage cycle performance.

Landscapes

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

Abstract

La présente invention concerne un additif appliqué dans un électrolyte de batterie. L'additif a la structure représentée par la formule (I) ci-dessous. Le substituant est représenté dans la description. La présente invention concerne en outre un électrolyte et une batterie utilisant l'additif. L'additif selon la présente invention peut être utilisé pour former un film CEI stable sur la surface d'une électrode positive, et améliore les performances de circulation de haute tension de la batterie.
PCT/CN2019/128699 2018-12-29 2019-12-26 Additif de formation de film d'électrode positive pour électrolyte de batterie, et électrolyte et batterie au lithium utilisant l'additif WO2020135584A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201811639257.6 2018-12-29
CN201811639257 2018-12-29

Publications (1)

Publication Number Publication Date
WO2020135584A1 true WO2020135584A1 (fr) 2020-07-02

Family

ID=71125741

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/128699 WO2020135584A1 (fr) 2018-12-29 2019-12-26 Additif de formation de film d'électrode positive pour électrolyte de batterie, et électrolyte et batterie au lithium utilisant l'additif

Country Status (2)

Country Link
CN (1) CN111384442B (fr)
WO (1) WO2020135584A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112366354B (zh) * 2020-12-02 2022-04-12 蜂巢能源科技有限公司 一种电解液及锂离子电池
CN114335724B (zh) * 2021-12-28 2023-06-27 广州天赐高新材料股份有限公司 一种高电压锂离子电池电解液及锂离子电池
TWI777912B (zh) * 2022-06-02 2022-09-11 台灣中油股份有限公司 鋰離子電池電解液及鋰離子電池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130164605A1 (en) * 2010-09-02 2013-06-27 Nec Corporation Secondary battery
CN104584309A (zh) * 2012-08-09 2015-04-29 三菱化学株式会社 非水系电解液和使用该非水系电解液的非水系电解液二次电池
KR20150130910A (ko) * 2014-05-14 2015-11-24 주식회사 엘지화학 전해액 및 이를 포함하는 이차전지

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101349750B1 (ko) * 2010-11-26 2014-01-10 솔브레인 주식회사 전해액 첨가제, 이를 포함하는 전해액 및 상기 전해액을 포함하는 리튬이차전지
CN102709588B (zh) * 2012-01-12 2016-04-27 宁德新能源科技有限公司 一种锂离子电池及其电解液
CN105720303B (zh) * 2014-12-05 2020-06-12 浙江蓝天环保高科技股份有限公司 一种含氟代羧酸酯的高电压锂离子电池电解液
CN104852087B (zh) * 2015-04-15 2017-03-01 宁德时代新能源科技股份有限公司 一种电解液添加剂及应用了该添加剂的锂离子电池
CN105161763A (zh) * 2015-08-03 2015-12-16 深圳新宙邦科技股份有限公司 一种锂离子电池非水电解液及锂离子电池
CN105762410B (zh) * 2016-04-01 2018-11-02 宁德新能源科技有限公司 一种非水电解液及使用该非水电解液的锂离子电池
CN107293781B (zh) * 2016-04-11 2020-06-12 宁德新能源科技有限公司 电解液及锂离子电池
CN105762413A (zh) * 2016-05-18 2016-07-13 东莞市凯欣电池材料有限公司 一种锂离子电池用非水电解质溶液及采用该电解液的锂离子电池
CN105826607B (zh) * 2016-05-25 2019-05-14 宁德新能源科技有限公司 一种电解液以及包括该电解液的锂离子电池
CN106025278B (zh) * 2016-07-01 2018-09-14 东莞市凯欣电池材料有限公司 一种高电压锂离子电池
CN108183260A (zh) * 2017-12-13 2018-06-19 中国科学院过程工程研究所 一种电解液和锂离子电池
CN108321434A (zh) * 2018-03-23 2018-07-24 安普瑞斯（无锡）有限公司 一种高电压锂离子电池电解液
CN108666623A (zh) * 2018-05-15 2018-10-16 北京科技大学 一种高电压锂离子电池的电解液
CN108987802B (zh) * 2018-06-15 2021-11-05 桑顿新能源科技(长沙)有限公司 一种高电压锂离子电池非水电解液

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130164605A1 (en) * 2010-09-02 2013-06-27 Nec Corporation Secondary battery
CN104584309A (zh) * 2012-08-09 2015-04-29 三菱化学株式会社 非水系电解液和使用该非水系电解液的非水系电解液二次电池
KR20150130910A (ko) * 2014-05-14 2015-11-24 주식회사 엘지화학 전해액 및 이를 포함하는 이차전지

Also Published As

Publication number Publication date
CN111384442B (zh) 2023-09-12
CN111384442A (zh) 2020-07-07

Similar Documents

Publication Publication Date Title
CN111628218B (zh) 一种锂离子电池及其制备方法
EP2168199B1 (fr) Électrolyte non-aqueux et dispositif électrochimique le comprenant
JP6751158B2 (ja) 非水電解液を用いたリチウムイオン電池
WO2016054843A1 (fr) Électrolyte non aqueux pour batterie au lithium-ion, et batterie au lithium-ion
CN111384443B (zh) 一种电池电解液添加剂及使用该添加剂的电解液和锂离子电池
US20220109191A1 (en) Non-aqueous electrolyte for a lithium ion battery and lithium ion battery
WO2020135584A1 (fr) Additif de formation de film d'électrode positive pour électrolyte de batterie, et électrolyte et batterie au lithium utilisant l'additif
WO2017020430A1 (fr) Électrolyte non aqueux de batterie au lithium-ion, et batterie au lithium-ion
US20240079652A1 (en) Lithium Ion Battery
CN111525190A (zh) 电解液及锂离子电池
WO2017020429A1 (fr) Électrolyte non aqueux pour batterie au lithium-ion à haute tension et batterie au lithium-ion
US20180294483A1 (en) Positive electrode plate and energy storage device
JP2001057234A (ja) 非水電解液および非水電解液二次電池
CN112928328A (zh) 一种含有硅烷基磺酰胺化合物的锂离子电池电解液和锂离子二次电池
US20180241085A1 (en) Nonaqueous electrolytic solution and nonaqueous electrolytic solution battery using the same
JP2001057235A (ja) 非水電解液および非水電解液二次電池
CN106340671B (zh) 锂离子电池及其电解液
CN111384438B (zh) 一种锂离子电池非水电解液及锂离子电池
CN113871712B (zh) 锂离子电池电解液及其制备方法和锂离子电池
CN111384439A (zh) 一种非水电解液及锂离子电池
WO2023279953A1 (fr) Électrolyte non aqueux et batterie
US20230411689A1 (en) Non-aqueous electrolyte for a lithium ion battery and lithium ion battery
JP5426809B2 (ja) 二次電池、二次電池を用いた電子機器及び輸送用機器
WO2020135694A1 (fr) Additif pour électrolyte de batterie, et électrolyte et batterie au lithium-ion utilisation celui-ci
CN111092264A (zh) 一种高电压电解液及含有该电解液的锂离子电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19905019

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19905019

Country of ref document: EP

Kind code of ref document: A1