WO2019024412A1 - 锂离子电池非水电解液及锂离子电池 - Google Patents

锂离子电池非水电解液及锂离子电池 Download PDF

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WO2019024412A1
WO2019024412A1 PCT/CN2017/119377 CN2017119377W WO2019024412A1 WO 2019024412 A1 WO2019024412 A1 WO 2019024412A1 CN 2017119377 W CN2017119377 W CN 2017119377W WO 2019024412 A1 WO2019024412 A1 WO 2019024412A1
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group
ion battery
lithium ion
compound
formula
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English (en)
French (fr)
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石桥
胡时光
邓朝晖
张�浩
刘春华
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Shenzhen Capchem Technology Co Ltd
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Shenzhen Capchem Technology Co Ltd
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Priority to US16/631,829 priority Critical patent/US11398644B2/en
Priority to EP17920123.1A priority patent/EP3664212B1/en
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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
    • H01M10/056—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D317/34—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • 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
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • 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
    • 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
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • 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 technical field of lithium ion battery electrolyte, and particularly relates to a lithium ion battery non-aqueous electrolyte and a lithium ion battery.
  • Lithium-ion batteries have made great progress in the field of portable electronic products due to their high operating voltage, high safety, long life and no memory effect. And with the development of new energy vehicles, lithium-ion batteries have shown great application prospects in power supply systems for new energy vehicles.
  • the non-aqueous electrolyte lithium ion battery is a key factor affecting the high and low temperature performance of the battery.
  • the additives in the non-aqueous electrolyte are particularly important for the performance of the high and low temperature performance of the battery. Because lithium ions in the positive electrode material of the battery are deintercalated during the initial charging of the lithium ion battery, they are embedded in the carbon negative electrode through the electrolyte.
  • the electrolyte reacts on the surface of the carbon negative electrode to produce compounds such as Li 2 CO 3 , Li 2 O, and LiOH, thereby forming a passivation film on the surface of the negative electrode, which is called a solid electrolyte interface film (SEI).
  • SEI solid electrolyte interface film
  • the SEI film formed during the initial charging process not only prevents the electrolyte from further decomposing on the surface of the carbon negative electrode, but also acts as a lithium ion tunneling, allowing only lithium ions to pass. Therefore, the SEI film determines the performance of the lithium ion battery.
  • Chinese Patent Application No. 03132755.9 discloses an electrolyte for a secondary battery of a sulfonate containing at least two sulfonyl groups, which helps to form a passivation layer at the electrode interface of the battery. The decomposition of solvent molecules is prevented, thereby improving the cycle performance of the battery while suppressing the gas production of the battery.
  • a non-aqueous electrolyte containing a sulfonyl group of a sulfonyl group can improve the normal temperature cycle performance of a lithium ion battery and reduce the high-temperature storage gas production of the battery to some extent, the battery high-temperature cycle The performance is obviously insufficient, and its high-temperature storage performance is still insufficient.
  • the object of the present invention is to provide a non-aqueous electrolyte for a lithium ion battery, which aims to solve the problems of poor high temperature cycle characteristics and poor storage performance of the existing lithium ion battery electrolyte.
  • Another object of the present invention is to provide a lithium ion battery comprising the above nonaqueous electrolyte of a lithium ion battery.
  • a lithium ion battery non-aqueous electrolyte comprising a compound of the formula A and a compound B of the formula II represented by the formula:
  • R 1 is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms or a fluorine-substituted alkylene group having 1 to 5 carbon atoms
  • R 2 is selected from the group consisting of 1 to 5 carbon atoms. Any one of an alkylene group, a fluorine-substituted alkylene group having 1 to 5 carbon atoms or a carbonyl group;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, a fluorine atom or a group having 1 to 5 carbon atoms.
  • the group having 1 to 5 carbon atoms is selected from a hydrocarbon group, a fluorohydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group or a cyano group-substituted hydrocarbon group.
  • the R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, and a trimethyl group. Silyloxy, cyano, or trifluoromethyl.
  • the compound A represented by the structural formula 1 is At least one of them;
  • the mass percentage of the compound A is from 0.1% to 2.0% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
  • the compound B has a mass percentage of 0.1% to 5.0% based on 100% of the total mass of the lithium ion battery nonaqueous electrolyte.
  • the nonaqueous electrolyte further contains at least one of an unsaturated cyclic carbonate, a fluorinated cyclic carbonate, and a cyclic sultone.
  • the unsaturated cyclic carbonate includes at least one of vinylene carbonate, ethylene carbonate, and methylene ethylene carbonate;
  • the fluorinated cyclic carbonate includes at least one of fluoroethylene carbonate, trifluoromethyl ethylene carbonate, and difluoroethylene carbonate;
  • the cyclic sultone lactone includes at least one of 1,3-propane sultone, 1,4-butane sultone, and acryl-1,3- sultone.
  • a lithium ion battery for isolating the separator of the positive electrode and the negative electrode, and an electrolyte solution, wherein the electrolyte solution is the lithium ion battery nonaqueous electrolyte solution described above.
  • the positive electrode comprises a positive active material
  • the active material of the positive electrode is selected from the group consisting of LiNi x Co y Mn z L (1-xyz) O 2 , LiCo x ' L (1-x') O 2 , LiNi x” At least one of L' y' Mn (2-x"-y') O 4 , Li z ' MPO 4 ; wherein L is Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe At least one of; 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x + y + z ⁇ 1, 0 ⁇ x' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6, 0.01 ⁇ y ' ⁇ 0.2;L' is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe; 0.5 ⁇ z' ⁇ 1, M is
  • the lithium ion battery non-aqueous electrolyte provided by the invention comprises the compound A of the formula I and the compound B of the formula II, and in the lithium ion battery, the compound A can be in the first charging process of the battery.
  • the surface of the negative electrode is decomposed in preference to the solvent molecules to form a passivation film, thereby inhibiting further decomposition of the electrolyte.
  • the inventors of the present invention found that the thermal stability of the passivation film is poor, and the passivation layer is easily destroyed during high-temperature cycling of the battery, resulting in deterioration of battery performance and poor high-temperature cycle performance.
  • Compound B can also be decomposed on the surface of the negative electrode material to form a passivation film, and the passivation film has high thermal stability. When both are used simultaneously, the reductive decomposition of compound A and compound B is formed on the surface of the negative electrode material.
  • the passivation film improves the thermal stability of the passivation film, thereby improving the high temperature cycle of the battery and further improving the high temperature storage performance.
  • the lithium ion battery provided by the present invention contains the nonaqueous electrolyte solution described above as an electrolyte solution, and thus has high temperature cycle performance and high temperature storage performance.
  • R 1 is selected from the group consisting of an alkylene group having 1 to 5 carbon atoms or a fluorine-substituted alkylene group having 1 to 5 carbon atoms
  • R 2 is selected from the group consisting of 1 to 5 carbon atoms. Any one of an alkylene group, a fluorine-substituted alkylene group having 1 to 5 carbon atoms or a carbonyl group;
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from hydrogen, a fluorine atom or a group having 1 to 5 carbon atoms.
  • the group of 1 to 5 carbon atoms is specifically selected from a hydrocarbon group, a fluorohydrocarbon group, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group or a cyano group-substituted hydrocarbon group.
  • the R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each independently selected from a hydrogen atom, a fluorine atom, a methyl group, an ethyl group, a methoxy group, an ethoxy group, and a trimethyl group. Silyloxy, cyano, or trifluoromethyl.
  • the compound A represented by the structural formula 1 is At least one of them (in order to facilitate the recording, in the present document, the codes A1 to A8 refer to the corresponding compounds).
  • the compound B represented by the formula II includes At least one of them (in order to facilitate the recording, in the present document, the code numbers B1 to B9 refer to the corresponding compounds).
  • the compound B represented by the above formula II may be produced by a polyol (such as erythritol, xylitol, etc.) and a carbonate (such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, etc.) under the action of a basic catalyst.
  • a polyol such as erythritol, xylitol, etc.
  • a carbonate such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, etc.
  • the transesterification reaction is further purified by recrystallization or column chromatography.
  • the specific synthetic route is as follows:
  • the preparation of the fluorine-containing compound in the compound B is carried out by fluorinating a mixture of the corresponding carbonate and F 2 /N 2 , followed by purification by recrystallization or column chromatography.
  • An example of its synthetic route is as follows:
  • the preparation of the cyano group-containing compound in the compound B is carried out by reacting the corresponding carbonate with a sulfonyl chloride, reacting with NaCN or KCN, and purifying by recrystallization or column chromatography.
  • An example of its synthetic route is as follows:
  • the preparation of the trimethylsiloxy compound in the compound B is carried out by subjecting the corresponding hydroxycarbonate to a substitution reaction with a nitrogen silane, followed by recrystallization or column chromatography.
  • An example of its synthetic route is as follows:
  • the mass percentage of the compound A is from 0.1% to 2.0% based on 100% of the total mass of the nonaqueous electrolyte of the lithium ion battery.
  • the compound B has a mass percentage of 0.1% to 5.0% based on 100% of the total mass of the lithium ion battery nonaqueous electrolyte.
  • the mass percentage of the compound B may be 0.1%, 0.2%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, 3 %, 3.5%, 4%, 4.5%, 5%.
  • the non-aqueous electrolyte solution in the technical solution of the present invention includes, in addition to the above two components, a non-aqueous electrolyte solution, and further comprises an unsaturated cyclic carbonate, a fluorocyclic carbonate, and a cyclic sultone. At least one of them.
  • the unsaturated cyclic carbonate is selected from at least one of vinylene carbonate (VC), ethylene carbonate (VEC), and methylene ethylene carbonate.
  • the fluorinated cyclic carbonate is at least one selected from the group consisting of fluoroethylene carbonate (FEC), trifluoromethyl ethylene carbonate, and difluoroethylene carbonate.
  • the cyclic sultone is selected from the group consisting of 1,3-propane sultone (1,3-PS), 1,4-butane sultone (1,4-BS), and propylene-1,3- At least one of sultone.
  • the lithium ion battery non-aqueous electrolyte contains a solvent and a lithium salt.
  • the solvent of the lithium ion battery non-aqueous electrolyte contains a cyclic carbonate and Chain carbonate.
  • the cyclic carbonate includes at least one of ethylene carbonate, propylene carbonate, and butylene carbonate.
  • the chain carbonate includes at least one of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and methyl propyl carbonate.
  • the lithium salt is not particularly limited in the present invention, and various kinds of existing ones may be employed.
  • the lithium salt may be selected from one or more of LiPF 6 , LiFSI, and LiBF 4 .
  • the content of the lithium salt may vary within a wide range.
  • the lithium ion battery has a lithium salt content of 0.1-15% in the nonaqueous electrolyte.
  • the compound A represented by the structural formula I can form a passivation film on the surface of the negative electrode in preference to the solvent molecule during the first charging of the battery, thereby suppressing the electrolyte solution. Further decomposition. However, the thermal stability of the passivation film is poor, and the passivation layer is easily destroyed during high temperature cycling or high temperature cycling of the battery.
  • the compound B represented by the structural formula II can also be decomposed on the surface of the negative electrode material to form a passivation film, and the passivation film has high thermal stability.
  • a passivation film formed by reductive decomposition of the compound A and the compound B can be formed on the surface of the negative electrode material, and the heat stability of the passivation film is improved. Sex, which improves the high temperature cycle of the battery, and its high temperature storage performance is further improved.
  • an embodiment of the present invention further provides a lithium ion battery.
  • the lithium ion battery includes a positive electrode, a negative electrode, a separator for isolating the positive electrode and the negative electrode, and an electrolyte, and the electrolyte is the lithium ion battery non-aqueous electrolyte described above.
  • the positive electrode includes a positive active material
  • the active material of the positive electrode is LiNi x Co y Mn z L (1-xyz) O 2 , LiCo x' L (1-x') O 2 , LiNi x" L At least one of ' y ' Mn (2-x"-y') O 4 , Li z ' MPO 4 ; wherein L is in Al, Sr, Mg, Ti, Ca, Zr, Zn, Si or Fe At least one; 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1, 0 ⁇ x + y + z ⁇ 1, 0 ⁇ x' ⁇ 1, 0.3 ⁇ x" ⁇ 0.6, 0.01 ⁇ y' ⁇ 0.2;L' is at least one of Co, Al, Sr, Mg, Ti, Ca, Zr, Zn, Si, Fe; 0.5 ⁇ z' ⁇ 1, M is at least one of Fe, Mn
  • the active material of the negative electrode is selected from the group consisting of artificial graphite and natural graphite. Of course, it is not limited to the two listed.
  • the separator is a conventional separator in the field of lithium ion batteries, and thus the present invention is not required to be further limited.
  • the lithium ion battery provided by the embodiment of the invention has good high temperature cycle performance and high temperature storage performance because it contains the above nonaqueous electrolyte.
  • an embodiment of the present invention uses a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery as an experimental battery.
  • the non-aqueous electrolyte of the present invention is Not only for 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 / artificial graphite battery.
  • a 4.2V LiNi 0.5 Co 0.2 Mn 0.3 O 2 /artificial graphite battery comprising a positive electrode, a negative electrode, a separator disposed between the positive electrode and the negative electrode, an electrolyte, and a battery can, wherein the electrolyte is non- The aqueous electrolyte, and including the compound A and the compound B, containing the mass percentage of the compound A and the compound B shown in Example 1 of Table 1, based on 100% by mass of the total mass of the nonaqueous electrolyte.
  • Comparative Examples 1 to 5 were the same as in Example 1 except that the additive components in Table 1 were different.
  • the lithium ion batteries prepared in the above Examples 1 to 14 and Comparative Examples 1 to 5 were subjected to corresponding performance tests, and the specific tests included high temperature cycle performance test and high temperature storage performance test.
  • the test method is as follows:
  • the lithium ion batteries prepared in Examples 1 to 14 and Comparative Examples 1 to 5 were placed in an oven at a constant temperature of 45 ° C, charged at a constant current of 1 C to 4.2 V, and charged at a constant voltage until the current dropped to 0.02 C, and then 1 C. The current was continuously discharged to 3.0 V, and the cycle was repeated, and the first discharge capacity and the last discharge capacity were recorded.
  • capacity retention rate last discharge capacity / first discharge capacity ⁇ 100%
  • the lithium ion battery after the formation was charged to 4.2 V at a normal temperature with a constant current of 1 C, and the initial discharge capacity and initial battery thickness of the battery were measured, and then stored in a 60 ° C environment for 30 days, discharged at 1 C to 3 V, and the battery was measured. Maintain capacity and recovery capacity and battery thickness after storage. Calculated as follows:
  • Battery capacity retention rate (%) retention capacity / initial capacity ⁇ 100%;
  • Battery capacity recovery rate (%) recovery capacity / initial capacity ⁇ 100%;
  • Thickness expansion ratio (%) (battery thickness after storage - initial battery thickness) / initial battery thickness ⁇ 100%.

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Abstract

为解决现有锂离子电池电解液高温循环性能不足的问题，本发明提供一种锂离子电池非水电解液。所述非水电解液包含结构式如式I所示的化合物A和式II所示的化合物B组分，其中，式I中，R 1选自碳原子数为1～5的亚烷基或碳原子数为1～5的氟取代的亚烷基；R 2选自碳原子数为1～5的亚烷基、碳原子数为1～5的氟取代的亚烷基或羰基中的任一种；式II中，R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢、氟原子或含1～5个碳原子的基团。所述非水电解液的化合物A和化合物B能在锂离子电池在负极材料表面形成还原分解复合而成的钝化膜，提高了钝化膜的热稳定性，从而改善电池的高温循环及储存性能。

Description

锂离子电池非水电解液及锂离子电池 技术领域
本发明属于锂离子电池电解液技术领域，尤其涉及一种锂离子电池非水电解液及锂离子电池。
背景技术
锂离子电池因其工作电压高、安全性高、长寿命、无记忆效应等特点，在便携式电子产品领域中取得了长足的发展。而且随着新能源汽车的发展，锂离子电池在新能源汽车用动力电源系统中表现出了巨大的应用前景。
在非水电解液锂离子电池中，非水电解液是影响电池高低温性能的关键因素。特别地，非水电解液中的添加剂对电池高低温性能的发挥尤其重要。因为在锂离子电池初始充电过程中，电池正极材料中的锂离子脱嵌出来，通过电解液嵌入碳负极中。由于其高反应性，电解液在碳负极表面反应产生Li 2CO 3、Li 2O、LiOH等化合物，从而在负极表面形成钝化膜，该钝化膜称为固体电解液界面膜(SEI)。在初始充电过程中形成的SEI膜，不仅阻止电解液进一步在碳负极表面分解，而且起到锂离子隧道作用，只允许锂离子通过。因此，SEI膜决定了锂离子电池性能的好坏。
为了提高锂离子电池的各项性能，许多科研者通过往电解液中添加不同的负极成膜添加剂(如碳酸亚乙烯酯，氟代碳酸乙烯酯，碳酸乙烯亚乙酯)来改善SEI膜的质量，从而改善电池的各项性能。
申请号为03132755.9的中国专利公开了一种至少含两个磺酰基的环磺酸酯的二次电池的电解液，该环状的磺酸酯有助于在电池电极界面上形成钝化层，阻止了溶剂分子的分解，从而改善电池的循环性能，同时抑制电池产气。虽然含两个磺酰基的环磺酸酯(如甲烷二磺酸亚甲酯)非水电解液能够在一定程度上 提高锂离子电池的常温循环性能及降低电池高温储存产气量，但是电池高温循环性能明显不足，且其高温存储性能仍不足。
发明内容
本发明的目的在于提供一种锂离子电池非水电解液，旨在解决现有锂离子电池电解液高温循环特性不佳和储存性能差等问题。
本发明的另一目的在于提供一种含有上述锂离子电池非水电解液的锂离子电池。
为了达到上述目的，本发明采用了如下的技术方案：
一种锂离子电池非水电解液，包含结构式如式I所示的化合物A和式II所示的化合物B组分：
Figure PCTCN2017119377-appb-000001
其中，所述式I中，R 1选自碳原子数为1～5的亚烷基或碳原子数为1～5的氟取代的亚烷基；R 2选自碳原子数为1～5的亚烷基、碳原子数为1～5的氟取代的亚烷基或羰基中的任一种；
所述式II中，R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢、氟原子或含1～5个碳原子的基团。
优选的，所述式II所示的化合物B中，含1～5个碳原子的基团选自烃基、 氟代烃基、含氧烃基、含硅烃基或含氰基取代的烃基。
优选的，所述R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢原子、氟原子、甲基、乙基、甲氧基、乙氧基、三甲基硅氧基、氰基、或三氟甲基。
优选的，所述结构式1所示化合物A为
Figure PCTCN2017119377-appb-000002
Figure PCTCN2017119377-appb-000003
Figure PCTCN2017119377-appb-000004
中的至少一种；
所述结构式II所示的化合物B为
Figure PCTCN2017119377-appb-000005
Figure PCTCN2017119377-appb-000006
中的至少一种。
优选的，以所述锂离子电池非水电解液的总质量为100％计，所述化合物A的质量百分含量为0.1％～2.0％。
优选的，以所述锂离子电池非水电解液的总质量为100％计，所述化合物B的质量百分含量为0.1％～5.0％。
优选的，所述非水电解液还包含不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯中的至少一种。
优选地，所述不饱和环状碳酸酯包括碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯中的至少一种；
所述氟代环状碳酸酯包括氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的至少一种；
所述环状磺酸内酯包括1,3-丙烷磺内酯、1,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯中的至少一种。
以及，一种锂离子电池，用于隔离所述正极和所述负极的隔膜、以及电解液，所述电解液为上述的锂离子电池非水电解液。
优选地，所述正极包括正极活性材料，所述正极的活性材料选自LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种；其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种；0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2；L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。
本发明提供的锂离子电池非水电解液，包括结构式如式I所示的化合物A和如式II所示的化合物B组分，在锂离子电池中，化合物A在电池首次充电过程中能够在负极表面优先于溶剂分子发生分解形成钝化膜，从而抑制电解液的进一步分解。但是本发明的发明人发现，该钝化膜的热稳定性较差，电池在高温循环过程中，钝化层容易被破坏，从而导致电池性能下降，高温循环性能较差。而化合物B也能在负极材料表面发生分解反应形成钝化膜，且该钝化膜的热稳定性高，两者同时使用时，在负极材料表面形成由化合物A和化合物B的还原分解复合而成的钝化膜，提高了钝化膜的热稳定性，从而改善电池的高温循环，并进一步提高了高温储存性能。
本发明提供的锂离子电池，含有采用了上述所述的非水电解液作为电解液，因此具有较好的高温循环性能及高温储存性能。
具体实施方式
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明实施例提供了一种锂离子电池非水电解液，包含结构式如式I所示的化合物A和式II所示的化合物B组分：
Figure PCTCN2017119377-appb-000007
Figure PCTCN2017119377-appb-000008
其中，所述式I中，R 1选自碳原子数为1～5的亚烷基或碳原子数为1～5的氟取代的亚烷基；R 2选自碳原子数为1～5的亚烷基、碳原子数为1～5的氟取代的亚烷基或羰基中的任一种；
所述式II中，R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢、氟素原子或含1～5个碳原子的基团。
优选地，上述式II中，所述1～5个碳原子的基团具体选自烃基、氟代烃基、含氧烃基、含硅烃基或含氰基取代的烃基。
进一步优选地，所述R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢原子、氟原子、甲基、乙基、甲氧基、乙氧基、三甲基硅氧基、氰基、或三氟甲基。
优选地，所述结构式1所示化合物A为
Figure PCTCN2017119377-appb-000009
Figure PCTCN2017119377-appb-000010
Figure PCTCN2017119377-appb-000011
中的至少一种，(为了便于记录，本文件中，代号A1～A8指代对应的化合物)。
优选地，所述结构式II所示的化合物B包括
Figure PCTCN2017119377-appb-000012
Figure PCTCN2017119377-appb-000013
Figure PCTCN2017119377-appb-000014
中的至少一种(为了便于记录，本文件中，代号B1～B9指代对应的化合物)。
上述式II所代表的化合物B可采用多元醇(如赤藓醇、木糖醇等)与碳酸酯(如碳酸二甲酯、碳酸二乙酯、碳酸乙烯酯等)在碱性催化剂作用下发生酯交换反应，再经重结晶或柱层析纯化制备，其具体合成路线示例如下：
Figure PCTCN2017119377-appb-000015
化合物B中含氟化合物的制备采用对应的碳酸酯与F 2/N 2的混合气氟化后，再经重结晶或柱层析纯化而得。其合成路线示例如下：
Figure PCTCN2017119377-appb-000016
化合物B中含氰基化合物的制备采用对应的碳酸酯与磺酰氯发生氯代反应后，再与NaCN或KCN反应，经重结晶或柱层析纯化而得。其合成路线示例如下：
Figure PCTCN2017119377-appb-000017
化合物B中含三甲基硅氧基化合物的制备采用对应的羟基碳酸酯与氮硅烷发生取代反应后，经重结晶或柱层析纯化而得。其合成路线示例如下：
Figure PCTCN2017119377-appb-000018
优选地，以所述锂离子电池非水电解液的总质量为100％计，所述化合物A的质量百分含量为0.1％～2.0％。
优选地，以所述锂离子电池非水电解液的总质量为100％计，所述化合物B的质量百分含量为0.1％～5.0％。例如，所述化合物B的质量百分含量可以为0.1％、0.2％、0.4％、0.5％、0.6％、0.8％、1％、1.2％、1.5％、1.8％、2％、2.5％、3％、3.5％、4％、4.5％、5％。
本发明技术方案中的非水电解液，除了包括上述两种物质组分外，还包括非水电解液还包含不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯中的至少一种。
优选地，所述不饱和环状碳酸酯选自碳酸亚乙烯酯(VC)、碳酸乙烯亚乙酯(VEC)、亚甲基碳酸乙烯酯中的至少一种。所述氟代环状碳酸酯选自氟代碳酸乙烯酯(FEC)、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的至少一种。所述环状磺酸内酯选自1,3-丙烷磺内酯(1,3-PS)、1,4-丁烷磺内酯(1,4-BS)、丙烯基-1,3-磺酸内酯中的至少一种。
如现有的，锂离子电池非水电解液中均含有溶剂以及锂盐，本发明方案中对于溶剂种类和含量没有特殊限制，例如该锂离子电池非水电解液的溶剂包含环状碳酸酯和链状碳酸酯。
优选地，所述环状碳酸酯包括碳酸乙烯酯、碳酸丙烯酯和碳酸丁烯酯中的至少一种。所述链状碳酸酯包括碳酸二甲酯、碳酸二乙酯、碳酸甲乙酯、碳酸甲丙酯中的至少一种。
本发明中对锂盐没有特殊限制，可采用现有的各种，例如所述锂盐可选自LiPF 6、LiFSI、LiBF 4中的一种或多种。所述锂盐的含量可在较大范围内变动，优选情况下，所述锂离子电池非水电解液中，锂盐的含量为0.1-15％。
以本发明的非水电解液作为锂离子电池的电解液时，通过结构式I所示的化合物A在电池首次充电过程中能够在负极表面优先于溶剂分子发生分解形成钝化膜，从而抑制电解液的进一步分解。但是该钝化膜的热稳定性较差，电池在高温循环或高温循环过程中，钝化层容易被破坏。结构式II所示化合物B也能在负极材料表面发生分解反应形成钝化膜，且钝化膜的热稳定性高。当结构 式I所示的化合物A和结构式II所示的化合物B同时使用时，能够在负极材料表面形成化合物A和化合物B的还原分解复合而成的钝化膜，提高了钝化膜的热稳定性，从而改善电池的高温循环，同时其高温储存性能也得到了进一步提高。
在本发明上述锂离子非水电解液的前提下，本发明实施例还提供了一种锂离子电池。
在一实施例中，所述锂离子电池，包括正极、负极、用于隔离所述正极和所述负极的隔膜、以及电解液，所述电解液为上述的锂离子电池非水电解液。
具体的，所述正极包括正极活性材料，所述正极的活性材料为LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种；其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种；0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2；L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。
所述负极的活性材料选自人造石墨、天然石墨。当然，不限于所列举的这两种。
所述隔膜为锂离子电池领域的常规隔膜，因此本发明不需要再做详细的限定。
本发明实施例提供的锂离子电池，由于含有上述非水电解液，因此具有较好的高温循环性能、高温存储性能。
为了更好的说明本发明的技术方案，下面结合具体实施例进行说明。
需要说明的是，本发明的实施例为了控制单一变量，均采用4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池作为实验电池，当然，应当说明的是，本发明的非水电解液并不仅仅适用于4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池。
实施例1
一种4.2V LiNi 0.5Co 0.2Mn 0.3O 2/人造石墨电池，包括正极、负极、设置在所述正极和所述负极之间的隔膜、电解液以及电池壳，其中，所述电解液为非水电解液，并且包括化合物A和化合物B，以所述非水电解液的总质量为100％计，含有表1实施例1所示质量百分含量的化合物A和化合物B。
实施例2～14
为了节省篇幅，实施例2～14均列于表1中。
对比例1～5
对比例1～5除了如表1中的添加成分不同之外，其余与实施例1均相同。
将上述实施例1～14及对比例1～5中制备的锂离子电池进行相应的性能测试，具体测试包括高温循环性能测试及高温储存性能测试。
测试的方法如下：
一、高温循环性能测试
将实施例1～14及对比例1～5制备的锂离子电池置于恒温45℃的烘箱中，以1C的电流恒流充电至4.2V，恒压充电至电流下降至0.02C，然后以1C的电流恒流放电至3.0V，如此循环，记录第1次的放电容量和最后一次的放电容量。
按下式计算高温循环的容量保持率：容量保持率＝最后一次的放电容量/第1次的放电容量×100％
二、高温储存性能测试
将化成后的锂离子电池在常温下用1C恒流恒压充至4.2V，测量电池初始放电容量及初始电池厚度，然后在60℃环境中储存30天后，以1C放电至3V，测量电池的保持容量和恢复容量及储存后电池厚度。计算公式如下：
电池容量保持率(％)＝保持容量/初始容量×100％；
电池容量恢复率(％)＝恢复容量/初始容量×100％；
厚度膨胀率(％)＝(储存后电池厚度-初始电池厚度)/初始电池厚度×100％。
表1实施例1～14及对比例1～5的各项数据
Figure PCTCN2017119377-appb-000019
Figure PCTCN2017119377-appb-000020
由表1的数据可知，比实施例1～10和对比例1，单独添加结构式I所示的化合物A时，电池的高温循环及高温储存性能较差，有待进一步提高。当结构式I所示的化合物与结构式II所示的化合物同时使用时，由于在负极形成了热稳定性更好的钝化膜，能够明显提高电池的高温循环及高温储存性能。同时可以看出，随结构式II所示的化合物B含量的提高，能够进一步改善电池的高温循环及储存性能。
通过对比实施例11～14与对比例2～5，在化合物A与VC、FEC、PS、双氟磺酰亚胺锂(LiFSI)基础上进一步添加化合物B，电池的高温循环及高温储存性能进一步提高。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明 的保护范围之内。

Claims (10)

  1. 一种锂离子电池非水电解液，其特征在于：包含结构式如式I所示的化合物A和式II所示的化合物B组分：
    Figure PCTCN2017119377-appb-100001
    其中，所述式I中，R 1选自碳原子数为1～5的亚烷基或碳原子数为1～5的氟取代的亚烷基；R 2选自碳原子数为1～5的亚烷基、碳原子数为1～5的氟取代的亚烷基或羰基中的任一种；
    所述式II中，R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢、氟原子或含1～5个碳原子的基团。
  2. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述式II所示的化合物B中，含1～5个碳原子的基团选自烃基、氟代烃基、含氧烃基、含硅烃基或含氰基取代的烃基。
  3. 如权利要求1～2任一项所述的锂离子电池非水电解液，其特征在于：所述R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自氢原子、氟原子、甲基、乙基、甲氧基、乙氧基、三甲基硅氧基、氰基、或三氟甲基。
  4. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述结构式1
    所示化合物A选自
    Figure PCTCN2017119377-appb-100002
    Figure PCTCN2017119377-appb-100003
    中的至少一种；
    所述结构式II所示的化合物B选自
    Figure PCTCN2017119377-appb-100004
    Figure PCTCN2017119377-appb-100005
    中的至少一种。
  5. 如权利要求1所述的锂离子电池非水电解液，其特征在于：以所述锂离子电池非水电解液的总质量为100％计，所述化合物A的质量百分含量为0.1％～2.0％。
  6. 如权利要求1所述的锂离子电池非水电解液，其特征在于：以所述锂离子电池非水电解液的总质量为100％计，所述化合物B的质量百分含量为0.1％～5.0％。
  7. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述非水电解液还包含不饱和环状碳酸酯、氟代环状碳酸酯、环状磺酸内酯中的至少一种。
  8. 如权利要求1所述的锂离子电池非水电解液，其特征在于：所述不饱和环状碳酸酯包括碳酸亚乙烯酯、碳酸乙烯亚乙酯、亚甲基碳酸乙烯酯中的至少一种；
    所述氟代环状碳酸酯包括氟代碳酸乙烯酯、三氟甲基碳酸乙烯酯、双氟代碳酸乙烯酯中的至少一种；
    所述环状磺酸内酯包括1,3-丙烷磺内酯、1,4-丁烷磺内酯、丙烯基-1,3-磺酸内酯中的至少一种。
  9. 一种锂离子电池，包括正极、负极、用于隔离所述正极和所述负极的隔膜、以及电解液，其特征在于：所述电解液为如权利要求1～8任一项所述的锂离子电池非水电解液。
  10. 如权利要求9所述的锂离子电池，其特征在于：所述正极包括正极活性材料，所述正极的活性材料选自LiNi xCo yMn zL (1-x-y-z)O 2、LiCo x’L (1-x’)O 2、LiNi x”L’ y’Mn (2-x”-y’)O 4、Li z’MPO 4中的至少一种；其中，L为Al、Sr、Mg、Ti、Ca、Zr、Zn、Si或Fe中的至少一种；0≤x≤1，0≤y≤1，0≤z≤1，0＜x+y+z≤1，0<x’≤1，0.3≤x”≤0.6，0.01≤y’≤0.2；L’为Co、Al、Sr、Mg、Ti、Ca、Zr、Zn、Si、Fe中的至少一种；0.5≤z’≤1，M为Fe、Mn、Co中的至少一种。
PCT/CN2017/119377 2017-07-31 2017-12-28 锂离子电池非水电解液及锂离子电池 Ceased WO2019024412A1 (zh)

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