WO2016004816A1 - 添加剂、电解质溶液及锂离子电池 - Google Patents

添加剂、电解质溶液及锂离子电池 Download PDF

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WO2016004816A1
WO2016004816A1 PCT/CN2015/081702 CN2015081702W WO2016004816A1 WO 2016004816 A1 WO2016004816 A1 WO 2016004816A1 CN 2015081702 W CN2015081702 W CN 2015081702W WO 2016004816 A1 WO2016004816 A1 WO 2016004816A1
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bismaleimide
maleimide
monomer
carbonate
additive
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PCT/CN2015/081702
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English (en)
French (fr)
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钱冠男
何向明
尚玉明
李建军
王莉
高剑
杨聚平
王要武
赵鹏
Original Assignee
江苏华东锂电技术研究院有限公司
清华大学
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Publication of WO2016004816A1 publication Critical patent/WO2016004816A1/zh
Priority to US15/400,599 priority Critical patent/US20170117584A1/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
    • 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
    • H01M10/052—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
    • H01M10/0568—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
    • 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 present invention relates to an additive, an electrolyte solution, and a lithium ion battery using the same.
  • Carbonate electrolyte is the most widely used lithium ion battery electrolyte.
  • Propylene carbonate (PC) has the characteristics of low melting point (-55 ° C), high boiling point (240 ° C), high dielectric constant, etc., especially excellent ion conductivity at low temperatures, and is an ideal electrolyte component.
  • the PC molecule will co-embed the graphite negative electrode during the discharge process of the battery, and as a result, it is difficult to form a stable solid electrolyte membrane (SEI) on the surface of the graphite negative electrode, which causes the graphite negative electrode material to be continuously peeled off and destroyed, which is very large.
  • SEI solid electrolyte membrane
  • An additive for a lithium ion battery which is a polymer obtained by polymerization of an organic diamine compound and a maleimide monomer, and the maleimide monomer includes a maleimide single At least one of a bulk, a bismaleimide monomer, a polymaleimide monomer, and a maleimide derivative monomer, the molecular formula of the organic diamine compound is Or formula (4) represents wherein R 3 and R 4 are divalent organic substituents,
  • An electrolyte solution comprising an electrolyte salt, a nonaqueous solvent and the above additive, the nonaqueous solvent comprising propylene carbonate.
  • a lithium ion battery includes a positive electrode, a negative electrode, a separator, and the above electrolyte solution.
  • the invention adopts a polymer obtained by polymerization of an organic diamine compound and a maleimide monomer as an additive, and modifying the electrolyte solution can effectively improve the structural damage caused by PC embedding of the graphite anode material.
  • the electrochemical stability and cycle performance of the electrochemical cell are improved.
  • Example 1 is a first charge and discharge curve of a lithium ion battery according to Example 1 of the present invention and Comparative Example 1.
  • Example 2 is a cycle performance curve of a lithium ion battery according to Example 2 of the present invention and Comparative Example 1.
  • Embodiments of the present invention provide an additive for a lithium ion battery, which is a polymer obtained by polymerization of an organic diamine compound and a maleimide monomer.
  • the maleimide monomer includes at least one of a maleimide monomer, a bismaleimide monomer, a polymaleimide monomer, and a maleimide derivative monomer.
  • the molecular formula of the maleimide monomer can be represented by the formula (1).
  • R 1 is a monovalent organic substituent, specifically, may be -R, -RNH 2 R, -C(O)CH 3 , -CH 2 OCH 3 , -CH 2 S(O)CH 3 , a monovalent form of a cyclolipid a group, a monovalent form of a substituted aromatic group, or a monovalent form of an unsubstituted aromatic group, such as -C 6 H 5 , -C 6 H 4 C 6 H 5 , or -CH 2 (C 6 H 4 ) CH 3 .
  • R is a hydrocarbon group of 1 to 6 carbons, preferably an alkyl group.
  • the substitution is preferably carried out by halogen, a 1 to 6 carbon alkyl group or a 1 to 6 carbon silane group.
  • the unsubstituted aromatic group is preferably a phenyl group, a methylphenyl group or a dimethylphenyl group.
  • the number of the aromatic benzene rings is preferably from 1 to 2.
  • the maleimide monomer may be selected from the group consisting of N-phenylmaleimide, N-(o-methylphenyl)-maleimide, N-(m-methylphenyl)- Maleimide, N-(p-methylphenyl)-maleimide, N-cyclohexanemaleimide, maleimide, maleimidophenol, Malay Imidazobenzocyclobutene, xylyl maleimide, N-methylmaleimide, vinyl maleimide, thiomaleimide, maleimide One or more of a ketone, a methylene maleimide, a maleimide methyl ether, a maleimido ethylene glycol, and a 4-maleimide phenyl sulfone.
  • the molecular formula of the bismaleimide monomer can be represented by the formula (2).
  • R 2 is a divalent organic substituent, and specifically, may be -R-, -RNH 2 R-, -C(O)CH 2 -, -CH 2 OCH 2 -, -C(O)-, -O- ,-OO-,-S-,-SS-,-S(O)-,-CH 2 S(O)CH 2 -,-(O)S(O)-, -R-Si(CH 3 ) 2 -O-Si(CH 3 ) 2 -R-, a divalent form of a cycloaliphatic group, a divalent form of a substituted aromatic group, or a divalent form of an unsubstituted aromatic group, such as a phenyl group ( -C 6 H 4 -), biphenyl (-C 6 H 4 C 6 H 4 -), substituted phenyl, substituted phenyl, -(C 6 H 4 )-R 5 - ( C 6 H 4 )-,
  • R 5 is -CH 2 -, -C(O)-, -C(CH 3 ) 2 -, -O-, -OO-, -S-, -SS-, -S(O)-, or -( O) S(O)-.
  • R is a hydrocarbon group of 1 to 6 carbons, preferably an alkyl group. The substitution is preferably carried out by halogen, a 1 to 6 carbon alkyl group or a 1 to 6 carbon silane group. The number of the aromatic benzene rings is preferably from 1 to 2.
  • the bismaleimide monomer may be selected from the group consisting of N,N'-bismaleimide-4,4'-diphenylmethane, 1,1'-(methylenebis-4 , 1-phenylene) bismaleimide, N,N'-(1,1'-diphenyl-4,4'-dimethylene) bismaleimide, N,N' -(4-methyl-1,3-phenylene) bismaleimide, 1,1'-(3,3'-dimethyl-1,1'-diphenyl-4,4' -Dimethylene) bismaleimide, N,N'-vinyl bismaleimide, N,N'-butenyl bismaleimide, N,N'-(1, 2-phenylene) bismaleimide, N,N'-(1,3-phenylene) bismaleimide, N,N'-bismaleimide sulfur, N,N '-Bismaleimide disulfide, N,N'-bismaleimide, N,N'-methylene
  • the maleimide derivative monomer can be obtained from the maleimide group in the above maleimide monomer, bismaleimide monomer or polymaleimide monomer
  • the H atom is substituted with a halogen atom.
  • the molecular formula of the organic diamine compound can be represented by the formula (3) or the formula (4).
  • R 3 and R 4 are divalent organic substituents.
  • R 3 may be -(CH 2 ) n -, -CH 2 -O-CH 2 -, -CH(NH)-(CH 2 ) n -, a divalent form of a cycloaliphatic group, divalent a substituted aromatic group in the form, or an unsubstituted aromatic group in a divalent form, such as a phenylene group (-C 6 H 4 -), a biphenyl group (-C 6 H 4 C 6 H 4 -), Substituted phenyl or substituted biphenyl.
  • the substitution is preferably carried out by halogen, a 1 to 6 carbon alkyl group or a 1 to 6 carbon silane group.
  • the number of the aromatic benzene rings is preferably from 1 to 2.
  • the organic diamine compound may include, but is not limited to, at least one of ethylenediamine, phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl ether.
  • the molecular weight of the polymer is between 1000 and 500,000.
  • the additive when the maleimide monomer is bismaleimide and the organic diamine compound is diaminodiphenylmethane, the additive may be represented by formula (5).
  • the additive is prepared by the following method:
  • a maleimide monomer and a solvent are mixed at a mass ratio of (0.01-1):1 to form a solution of a maleimide monomer, preferably, the maleimide.
  • the mass ratio of monomer to solvent is (0.1 ⁇ 0.5):1;
  • the molar ratio of the maleimide monomer to the organic diamine compound is (0.1 to 10): 1, preferably (0.5 to 4): 1.
  • the solution of the organic diamine compound is formed by dissolving the organic diamine compound in a solvent in advance, and the mass ratio of the organic diamine compound to the solvent is (0.01 to 1): 1, preferably (0.1 to 0.5). ):1.
  • the solution of the organic diamine compound can be transported to the solution of the maleimide monomer at a certain rate by the transfer pump, and after the completion of the delivery, stirring is continued for a certain period of time to complete the reaction, and the stirring is performed.
  • the time may be from 0.5 to 48 hours, preferably from 1 to 24 hours.
  • the solvent is an organic solvent capable of dissolving the maleimide monomer and the organic diamine compound, for example, ⁇ -butyrolactone, propylene carbonate, and N-methylpyrrolidone (NMP).
  • Embodiments of the present invention provide an electrolyte solution including an electrolyte salt, a nonaqueous solvent, and an additive.
  • the electrolyte salt and the additive are both dissolved in the nonaqueous solvent.
  • the mass-to-volume concentration of the additive in the electrolyte solution may be from 0.01% to 10% (w/v), preferably from 0.1% to 5%.
  • electrolyte salts and non-aqueous solvents may be employed depending on the use of the electrolyte solution.
  • the nonaqueous solvent may include one or more of a cyclic carbonate, a chain carbonate, a cyclic ether, a chain ether, a nitrile, and an amide, such as ethylene carbonate, diethyl carbonate, and carbonic acid.
  • Propylene ester dimethyl carbonate, ethyl methyl carbonate, butylene carbonate, ⁇ -butyrolactone, ⁇ -valerolactone, dipropyl carbonate, N-methylpyrrolidone (NMP), N-methylformamide , N-methylacetamide, dimethylformamide, diethylformamide, diethyl ether, acetonitrile, propionitrile, anisole, succinonitrile, adiponitrile, glutaronitrile, dimethyl sulfoxide, sub Dimethyl sulfate, vinylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, fluoroethylene carbonate, chlorocarbonate, anhydride, sulfolane, methoxymethylsulfone, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, methyl acetate, ethyl acetate, propyl acetate, N
  • the electrolyte salt may be a lithium salt, and is not limited in kind, such as lithium chloride (LiCl), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium methanesulfonate (LiCH 3 SO 3 ), trifluoromethanesulfonate.
  • LiCl lithium chloride
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • LiCH 3 SO 3 lithium methanesulfonate
  • trifluoromethanesulfonate LiCH 3 SO 3
  • Lithium acid LiCF 3 SO 3
  • LiAsF 6 lithium hexafluoroarsenate
  • LiSbF 6 lithium hexafluoroantimonate
  • LiClO 4 lithium perchlorate
  • Li[BF 2 (C 2 O 4 )] One or more of Li[PF 2 (C 2 O 4 ) 2 ], Li[N(CF 3 SO 2 ) 2 ], Li[C(CF 3 SO 2 ) 3 ], and lithium bis(oxalate)borate (LiBOB)kind.
  • the embodiment of the invention further provides an electrochemical cell comprising a positive electrode, a negative electrode, a separator and the electrolyte solution.
  • the positive electrode and the negative electrode are spaced apart from each other by the separator.
  • the positive electrode may further include a positive electrode current collector and a positive electrode material layer formed on the surface of the positive electrode current collector.
  • the negative electrode may further include a negative electrode current collector and a negative electrode material layer formed on the surface of the negative electrode current collector.
  • the negative electrode material layer is opposed to the above positive electrode material layer and disposed at intervals by the separator.
  • the positive electrode material layer may include a positive electrode active material, specifically a lithium-transition metal oxide having a layer structure, a lithium-transition metal oxide having a spinel structure, and an olivine. At least one of lithium-transition metal oxides of a type structure, for example, olivine-type lithium iron phosphate, layered structure lithium cobaltate, layered structure lithium manganate, spinel-type lithium manganate, lithium nickel manganese oxide And lithium nickel cobalt manganese oxide.
  • the anode material layer may include at least one of an anode active material such as lithium titanate, graphite, phase carbon microspheres (MCMB), acetylene black, microbead carbon, carbon fibers, carbon nanotubes, and cracked carbon.
  • the positive electrode material layer and the negative electrode material layer may include a conductive agent and a binder, respectively.
  • the conductive agent may be one or more of a carbon material such as carbon black, a conductive polymer, acetylene black, carbon fiber, carbon nanotubes, and graphite.
  • the binder may be one of polyvinylidene fluoride (PVDF), poly(vinylidene fluoride), polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene monomer, and styrene butadiene rubber (SBR). Or a variety.
  • the separator may be a polyolefin porous film, a modified polypropylene felt, a polyethylene felt, a glass fiber felt, an ultrafine glass fiber paper vinylon felt or a nylon felt and a wettable polyolefin microporous film welded or bonded. a composite film.
  • the polymer is added as an additive to the electrolyte solution of the lithium ion battery, specifically, propylene carbonate and diethyl carbonate are mixed as a solvent, LiPF 6 is dissolved in the solvent, and the concentration of LiPF 6 is 1 mol/L, and propylene carbonate
  • the volume ratio to diethyl carbonate was 3:2, and it was set as an electrolyte.
  • the additive was added to the electrolyte, and the additive had a mass to volume concentration of 1% (w/v) in the electrolyte.
  • the lithium battery is assembled, the positive electrode is metal lithium, the negative electrode is graphite, and is charged and discharged with a constant current of 0.2 C in a voltage range of 0.01 V to 2 V.
  • Example 1 The difference from Example 1 was only that the additive was not added to the electrolyte solution.
  • the first discharge curve of the lithium ion battery containing no additive in the electrolyte solution of Comparative Example 1 shows a platform at about 0.7V, indicating that a serious PC co-intercalation phenomenon occurs, causing the graphite negative electrode to peel off and causing irreversible damage.
  • the first discharge voltage of the lithium ion battery containing the additive in the electrolyte solution of Example 1 is rapidly decreased to about 0 V, and the characteristic voltage platform ( ⁇ 0.7 V) of the PC co-intercalated graphite can be observed to be shortened, so that the additive has improved PC co-embedding.
  • the role of graphite is described in the role of graphite.
  • the electrolyte solution of the lithium ion battery is added, specifically, propylene carbonate and diethyl carbonate are mixed as a solvent, LiPF 6 is dissolved in the solvent, and the concentration of LiPF 6 is 1.2 mol/L.
  • the volume ratio of propylene carbonate to diethyl carbonate was 2:2, and it was set as an electrolyte.
  • the additive was added to the electrolyte, and the additive had a mass to volume concentration of 1% (w/v) in the electrolyte.
  • the lithium battery is assembled, the positive electrode is metal lithium, the negative electrode is graphite, and is charged and discharged with a constant current of 0.2 C in a voltage range of 0.01 V to 2 V.
  • the addition of the additive of the embodiment 2 can not only improve the PC co-intercalation phenomenon, but the discharge specific capacity can reach about 314 mAh/g after 60 cycles of the battery, and the discharge of the lithium ion battery of the comparative example 1 after 60 cycles.
  • the specific capacity of 308 mAh / g is equivalent or even slightly higher, indicating that the addition of the additive does not adversely affect the cycle performance of the lithium ion battery.

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Abstract

本发明涉及一种用于锂离子电池的添加剂，该添加剂是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物，该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。本发明还涉及一种电解质溶液及锂离子电池。

Description

添加剂、电解质溶液及锂离子电池 技术领域
本发明涉及一种添加剂、电解质溶液及应用该电解质溶液的锂离子电池。
背景技术
碳酸酯类电解液是目前应用最广泛的锂离子电池电解液。碳酸丙烯酯（PC）具有低熔点（-55℃）、高沸点（240℃）、高介电常数等特点，尤其在低温下具有优异的离子传导能力，是一种理想的电解液组分。但是，PC分子会在电池放电过程中与石墨负极发生共嵌现象，结果石墨负极表面难以形成稳定的固体电解质膜(SEI)，从而导致石墨负极材料不断发生剥落而遭到破坏，这在很大程度上限制了PC作为电解液组分的应用。
发明内容
有鉴于此，确有必要提供一种添加剂、应用该添加剂的电解质溶液及应用该电解质溶液的锂离子电池，该添加剂能够改善石墨负极材料因PC嵌入而导致的结构破坏问题。
一种用于锂离子电池的添加剂，是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物，该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种，该有机二胺类化合物的分子通式由式(3)或式(4)表示，其中R3与R4为二价有机取代基，
Figure WO070-appb-I000001
(3)；
Figure WO070-appb-I000002
(4)。
一种电解质溶液，包括电解质盐、非水溶剂及上述添加剂，该非水溶剂包括碳酸丙烯酯。
一种锂离子电池，包括正极、负极、隔膜及上述电解质溶液。
本发明采用有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物作为添加剂，对电解质溶液进行改性，可以有效改善石墨负极材料因PC嵌入而导致的结构破坏问题，提高了电化学电池的电化学稳定性及循环性能。
 附图说明
图1为本发明实施例1及对比例1的锂离子电池的首次充放电曲线。
图2为本发明实施例2及对比例1的锂离子电池的循环性能曲线。
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例对本发明提供的电解质溶液及应用该电解质溶液的锂离子电池作进一步的详细说明。
本发明实施方式提供一种用于锂离子电池的添加剂，该添加剂是由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物。
该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种。
该马来酰亚胺单体的分子通式可以由式(1)表示。
Figure WO070-appb-I000003
(1)
R1为单价有机取代基，具体地，可以为-R, -RNH2R, -C(O)CH3，-CH2OCH3, -CH2S(O)CH3, 单价形式的环脂族基团，单价形式的取代芳香族基团，或单价形式的未取代芳香族基团，如-C6H5, -C6H4C6H5，或-CH2(C6H4)CH3。R为1~6个碳的烃基，优选为烷基。所述取代优选是以卤素，1~6个碳的烷基或1~6个碳的硅烷基进行取代。该未取代芳香族基团优选为苯基、甲基苯基或二甲基苯基。该芳香族的苯环的数量优选为1~2个。
具体地，该马来酰亚胺单体可以选自N-苯基马来酰亚胺、N-(邻甲基苯基)-马来酰亚胺、N-(间甲基苯基)-马来酰亚胺、N-(对甲基苯基)-马来酰亚胺、N-环己烷基马来酰亚胺、马来酰亚胺、马来酰亚胺基酚、马来酰亚胺基苯并环丁烯、二甲苯基马来酰亚胺、N-甲基马来酰亚胺、乙烯基马来酰亚胺、硫代马来酰亚胺、马来酰亚胺酮、亚甲基马来酰亚胺、马来酰亚胺甲醚、马来酰亚胺基乙二醇及4-马来酰亚胺苯砜中的一种或多种。
该双马来酰亚胺单体的分子通式可以由式(2)表示。
Figure WO070-appb-I000004
(2)
R2为二价有机取代基，具体地，可以为-R-，-RNH2R-，-C(O)CH2-，-CH2OCH2-，-C(O)-，-O-，-O-O-，-S-，-S-S-，-S(O)-，-CH2S(O)CH2-，-(O)S(O)-， -R-Si(CH3)2-O-Si(CH3)2-R-，二价形式的环脂族基团，二价形式的取代芳香族基团，或二价形式的未取代芳香族基团，如伸苯基（-C6H4-），伸联苯基（-C6H4C6H4-），取代的伸苯基，取代的伸联苯基，-(C6H4)-R5-(C6H4)-，-CH2(C6H4)CH2-，或-CH2(C6H4)(O)-。R5为-CH2-，-C(O)-，-C(CH3)2-，-O-，-O-O-，-S-，-S-S-，-S(O)-，或-(O)S(O)-。R为1~6个碳的烃基，优选为烷基。所述取代优选是以卤素，1~6个碳的烷基或1~6个碳的硅烷基进行取代。该芳香族的苯环的数量优选为1~2个。
具体地，该双马来酰亚胺单体可以选自N,N’-双马来酰亚胺-4,4’-二苯基代甲烷、1,1’-(亚甲基双-4,1-亚苯基)双马来酰亚胺、N,N’-(1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-(4-甲基-1,3-亚苯基)双马来酰亚胺、1,1’-(3,3’-二甲基-1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-乙烯基双马来酰亚胺、N,N’-丁烯基双马来酰亚胺、N,N’-(1,2-亚苯基)双马来酰亚胺、N,N’-(1,3-亚苯基)双马来酰亚胺、N,N’-双马来酰亚胺硫、N,N’-双马来酰亚胺二硫、N,N’-双马来酰亚胺亚胺酮、N,N’-亚甲基双马来酰亚胺、双马来酰亚胺甲醚、1,2-双马来酰亚胺基-1,2-乙二醇、N,N’-4,4’-二苯醚-双马来酰亚胺及4,4’-双马来酰亚胺-二苯砜中的一种或多种。
该马来酰亚胺类衍生物单体可通过将上述马来酰亚胺单体、双马来酰亚胺单体或多马来酰亚胺单体中马来酰亚胺基团中的H原子以卤素原子取代。
该有机二胺类化合物的分子通式可以由式(3)或式(4)表示。
Figure WO070-appb-I000005
(3)
Figure WO070-appb-I000006
(4)
其中R3与R4为二价有机取代基。
具体地，R3可以为-(CH2)n-，-CH2-O-CH2-，-CH(NH)-(CH2)n-，二价形式的环脂族基团，二价形式的取代芳香族基团，或二价形式的未取代芳香族基团，如伸苯基（-C6H4-），伸联苯基（-C6H4C6H4-），取代的伸苯基或取代的伸联苯基。R4可以为-(CH2)n-，-O-，-S-，-S-S-，-CH2-O-CH2-，-CH(NH)-(CH2)n-或-CH(CN)(CH2)n-。n=1~12。所述取代优选是以卤素，1~6个碳的烷基或1~6个碳的硅烷基进行取代。该芳香族的苯环的数量优选为1~2个。
具体地，该有机二胺类化合物可以包括但不限于乙二胺、苯二胺、二氨基二苯甲烷及二氨基二苯醚中的至少一种。
该聚合物的分子量介于1000~500000之间。
在一实施例中，当该马来酰亚胺单体为双马来酰亚胺，有机二胺类化合物为二氨基二苯甲烷，该添加剂可以由式(5)表示。
Figure WO070-appb-I000007
(5)
该添加剂通过以下方法制备：
S1，将马来酰亚胺类单体与溶剂以质量比为(0.01~1):1的比例混合，形成马来酰亚胺类单体的溶液，优选地，该马来酰亚胺类单体与溶剂的质量比为(0.1~0.5):1；
S2，将该马来酰亚胺类单体的溶液加热30℃~180℃之间，优选为50℃~150℃之间；以及
S3，将有机二胺类化合物的溶液与加热后的该马来酰亚胺类单体的溶液混合并搅拌反应，得到所述聚合物，也就是该添加剂。
该马来酰亚胺类单体与该有机二胺类化合物的摩尔比为(0.1~10):1，优选为(0.5~4):1。该有机二胺类化合物的溶液是将所述有机二胺类化合物预先溶解在溶剂中形成，该有机二胺类化合物与溶剂的质量比为(0.01~1):1，优选为(0.1~0.5):1。在该步骤S3中，该有机二胺类化合物的溶液可以通过输送泵以一定速率输送至马来酰亚胺类单体的溶液中，输送完毕后持续搅拌一定时间，使反应充分进行，该搅拌时间可以为0.5~48小时，优选为1~24小时。该溶剂为能够溶解该马来酰亚胺类单体与该有机二胺类化合物的有机溶剂，例如γ-丁内酯、碳酸丙烯酯及N-甲基吡咯烷酮(NMP)。
本发明实施方式提供一种电解质溶液，包括电解质盐、非水溶剂及添加剂。该电解质盐及该添加剂均溶于该非水溶剂中。该添加剂在该电解质溶液中的质量体积比浓度可以为0.01%-10%（w/v），优选为0.1%-5%。
根据该电解质溶液的用途不同，可采用不同的电解质盐和非水溶剂。
该非水溶剂可包括环状碳酸酯、链状碳酸酯、环状醚类、链状醚类、腈类及酰胺类中的一种或多种，如碳酸乙烯酯、碳酸二乙酯、碳酸丙烯酯、碳酸二甲酯、碳酸甲乙酯、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、碳酸二丙酯、N-甲基吡咯烷酮(NMP)、N-甲基甲酰胺、N-甲基乙酰胺、二甲基甲酰胺、二乙基甲酰胺、二乙醚、乙腈、丙腈、苯甲醚、丁二腈、己二腈、戊二腈、二甲亚砜、亚硫酸二甲酯、碳酸亚乙烯酯、碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、氟代碳酸乙烯酯、氯代碳酸丙烯酯、酸酐、环丁砜、甲氧基甲基砜、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丙酸乙酯、丙酸甲酯、二甲基甲酰胺、1,3-二氧戊烷、1,2-二乙氧基乙烷、1,2-二甲氧基乙烷、或1,2-二丁氧基中的一种或几种的组合。
该电解质盐可以为锂盐，种类不限，例如氯化锂（LiCl）、六氟磷酸锂（LiPF6）、四氟硼酸锂（LiBF4）、甲磺酸锂（LiCH3SO3）、三氟甲磺酸锂（LiCF3SO3）、六氟砷酸锂（LiAsF6）、六氟锑酸锂（LiSbF6）、高氯酸锂（LiClO4）、Li[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3]及双草酸硼酸锂（LiBOB）中的一种或多种。
本发明实施例进一步提供一种电化学电池，包括正极、负极、隔膜及所述电解质溶液。该正极与负极通过所述隔膜相互间隔。所述正极可进一步包括一正极集流体及形成于该正极集流体表面的正极材料层。所述负极可进一步包括一负极集流体及形成于该负极集流体表面的负极材料层。该负极材料层与上述正极材料层相对且通过所述隔膜间隔设置。
当该电化学电池为锂离子电池时，该正极材料层可包括正极活性物质，具体可以为层状结构的锂-过渡金属氧化物，尖晶石型结构的锂-过渡金属氧化物以及橄榄石型结构的锂-过渡金属氧化物中的至少一种，例如，橄榄石型磷酸铁锂、层状结构钴酸锂、层状结构锰酸锂、尖晶石型锰酸锂、锂镍锰氧化物及锂镍钴锰氧化物。该负极材料层可包括负极活性物质，如钛酸锂、石墨、相碳微球(MCMB)、乙炔黑、微珠碳、碳纤维、碳纳米管及裂解碳中的至少一种。
另外，该正极材料层和负极材料层可分别包括导电剂及粘结剂。该导电剂可以为碳素材料，如碳黑、导电聚合物、乙炔黑、碳纤维、碳纳米管及石墨中的一种或多种。该粘结剂可以是聚偏氟乙烯(PVDF)、聚偏（二）氟乙烯、聚四氟乙烯(PTFE)、氟类橡胶、三元乙丙橡胶及丁苯橡胶(SBR)中的一种或多种。
所述隔离膜可以为聚烯烃多孔膜、改性聚丙烯毡、聚乙烯毡、玻璃纤维毡、超细玻璃纤维纸维尼纶毡或尼龙毡与可湿性聚烯烃微孔膜经焊接或粘接而成的复合膜。
实施例1
添加剂的制备：将4g双马来酰亚胺及2.207g二氨基二苯甲烷溶解在NMP中，去除溶液中的氧气，加热至130℃反应6小时，冷却后用乙醇沉淀，洗涤烘干，得到的添加剂由式(5)表示。
将该聚合物作为添加剂加入锂离子电池的电解质溶液中，具体为将碳酸丙烯酯与碳酸二乙酯混合作为溶剂，LiPF6溶于该溶剂中，LiPF6浓度为1 mol/L，碳酸丙烯酯与碳酸二乙酯的体积比为3:2，配置成电解液。向该电解液中加入所述添加剂，该添加剂在该电解液中的质量体积比浓度为1% （w/v）。组装锂电池，正极为金属锂，负极为石墨，在0.01V~2V电压范围之间以0.2C电流恒流充放电。
对比例1
与实施例1区别仅在不在电解质溶液中加入所述添加剂。
请参阅图1，对比例1电解质溶液未包含添加剂的锂离子电池首次放电曲线在0.7V左右出现一平台，表明发生严重的PC共嵌石墨现象，导致石墨负极发生剥落，造成不可逆的损坏。而实施例1电解质溶液含添加剂的锂离子电池的首次放电电压迅速下降为0V左右，可观察到PC共嵌石墨的特征电压平台（~0.7V）缩短，因此可说明该添加剂有改善PC共嵌石墨的作用。
实施例2
采用与实施例1相同的添加剂，加入锂离子电池的电解质溶液中，具体为将碳酸丙烯酯与碳酸二乙酯混合作为溶剂，LiPF6溶于该溶剂中，LiPF6浓度为1.2 mol/L，碳酸丙烯酯与碳酸二乙酯的体积比为2:2，配置成电解液。向该电解液中加入所述添加剂，该添加剂在该电解液中的质量体积比浓度为1%（w/v）。组装锂电池，正极为金属锂，负极为石墨，在0.01V~2V电压范围之间以0.2C电流恒流充放电。
请参阅图2，实施例2加入添加剂后不仅可以使PC共嵌石墨现象得以改善，电池60次循环后放电比容量可以达到约314mAh/g，与对比例1的锂离子电池60次循环后放电比容量308mAh/g相当甚至略高，说明该添加剂的加入不会对锂离子电池的循环性能产生不利影响。
实施例3
添加剂的制备：将3.2 g N-苯基马来酰亚胺及2.34 g二氨基二苯甲烷溶解在NMP中，去除溶液中的氧气，加热至120℃反应8小时，冷却后用乙醇沉淀，洗涤烘干，得到所述添加剂。将该聚合物作为添加剂加入锂离子电池的电解质溶液中，与实施例1相同条件组装锂离子电池，并进行电池循环性能测试。经测试，通过在锂离子电池电解液中加入添加剂可以改善PC共嵌石墨的作用，且60次循环后放电比容量可以达到约312mAh/g。
实施例4
添加剂的制备：将4g N,N’-乙烯基双马来酰亚胺及2.75 g二氨基二苯甲烷溶解在NMP中，去除溶液中的氧气，加热至135℃反应7小时，冷却后用乙醇沉淀，洗涤烘干，得到所述添加剂由式(5)表示。将该聚合物作为添加剂加入锂离子电池的电解质溶液中，与实施例1相同条件组装锂离子电池，并进行电池循环性能测试。经测试，通过在锂离子电池电解液中加入添加剂可以改善PC共嵌石墨的作用，且60次循环后放电比容量可以达到约311mAh/g。
实施例5
添加剂的制备：将4.75g由式(6)表示的双马来酰亚胺及2.26 g二氨基二苯醚溶解在NMP中，去除溶液中的氧气，加热至155℃反应6小时，冷却后用乙醇沉淀，洗涤烘干，得到所述添加剂。将该聚合物作为添加剂加入锂离子电池的电解质溶液中，与实施例1相同条件组装锂离子电池，并进行电池循环性能测试。经测试，通过在锂离子电池电解液中加入添加剂可以改善PC共嵌石墨的作用，且60次循环后放电比容量可以达到约317mAh/g。
Figure WO070-appb-I000008
(6)
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。

Claims (16)

  1. 一种添加剂，该添加剂用于锂离子电池，其特征在于，该添加剂由有机二胺类化合物与马来酰亚胺类单体通过聚合反应得到的聚合物，该马来酰亚胺类单体包括马来酰亚胺单体、双马来酰亚胺单体、多马来酰亚胺单体及马来酰亚胺类衍生物单体中的至少一种，该有机二胺类化合物的分子通式由式(3)或式(4)表示，其中R3与R4为二价有机取代基，
    Figure WO070-appb-I000009
    (3)；
    Figure WO070-appb-I000010
    (4)。
  2. 如权利要求1所述的添加剂，其特征在于，其中，R3为-(CH2)n-，-CH2-O-CH2-，-CH(NH)-(CH2)n-，伸苯基，伸联苯基，取代的伸苯基，取代的伸联苯基，二价形式的环脂族基团，R4为-(CH2)n-，-O-，-S-，-S-S-，-CH2-O-CH2-，-CH(NH)-(CH2)n-或-CH(CN)(CH2)n-，n=1~12。
  3. 如权利要求1所述的添加剂，其特征在于，该有机二胺类化合物包括乙二胺、苯二胺、二氨基二苯甲烷及二氨基二苯醚中的至少一种。
  4. 如权利要求1所述的添加剂，其特征在于，该马来酰亚胺单体的分子通式由式(1)表示，其中R1为单价有机取代基：
    Figure WO070-appb-I000011
    (1) 。
  5. 如权利要求4所述的添加剂，其特征在于，R1为-R, -RNH2R, -C(O)CH3，-CH2OCH3, -CH2S(O)CH3, -C6H5, -C6H4C6H5，-CH2(C6H4)CH3，或单价形式的环脂族；R为1-6个碳的烃基。
  6. 如权利要求1所述的添加剂，其特征在于，该马来酰亚胺单体选自N-苯基马来酰亚胺、N-(邻甲基苯基)-马来酰亚胺、N-(间甲基苯基)-马来酰亚胺、N-(对甲基苯基)-马来酰亚胺、N-环己烷基马来酰亚胺、马来酰亚胺、马来酰亚胺基酚、马来酰亚胺基苯并环丁烯、二甲苯基马来酰亚胺、N-甲基马来酰亚胺、乙烯基马来酰亚胺、硫代马来酰亚胺、马来酰亚胺酮、亚甲基马来酰亚胺、马来酰亚胺甲醚、马来酰亚胺基乙二醇及4-马来酰亚胺苯砜中的一种或多种。
  7. 如权利要求1所述的添加剂，其特征在于，该双马来酰亚胺单体的分子通式由式(2)表示，其中R2为二价有机取代基：
    Figure WO070-appb-I000012
    (2)。
  8. 如权利要求7所述的添加剂，其特征在于，R2为-R-，-RNH2R-，-C(O)CH2-，-CH2OCH2-，-C(O)-，-O-，-O-O-，-S-，-S-S-，-S(O)-，-CH2S(O)CH2-，-(O)S(O)-，-CH2(C6H4)CH2-，-CH2(C6H4)(O)-，-R-Si(CH3)2-O-Si(CH3)2-R-，-C6H4-，-C6H4C6H4-，二价形式的环脂族基团，或-(C6H4)-R5-(C6H4)-，R5为-CH2-，-C(O)-，-C(CH3)2-，-O-，-O-O-，-S-，-S-S-，-S(O)-，或-(O)S(O)-，R为1~6个碳的烃基。
  9. 如权利要求1所述的添加剂，其特征在于，该双马来酰亚胺单体选自N,N’-双马来酰亚胺-4,4’-二苯基代甲烷、1,1’-(亚甲基双-4,1-亚苯基)双马来酰亚胺、N,N’-(1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-(4-甲基-1,3-亚苯基)双马来酰亚胺、1,1’-(3,3’-二甲基-1,1’-二苯基-4,4’-二亚甲基)双马来酰亚胺、N,N’-乙烯基双马来酰亚胺、N,N’-丁烯基双马来酰亚胺、N,N’-(1,2-亚苯基)双马来酰亚胺、N,N’-(1,3-亚苯基)双马来酰亚胺、N,N’-双马来酰亚胺硫、N,N’-双马来酰亚胺二硫、N,N’-双马来酰亚胺亚胺酮、N,N’-亚甲基双马来酰亚胺、双马来酰亚胺甲醚、1,2-双马来酰亚胺基-1,2-乙二醇、N,N’-4,4’-二苯醚-双马来酰亚胺及4,4’-双马来酰亚胺-二苯砜中的一种或多种。
  10. 如权利要求1所述的添加剂，其特征在于，该马来酰亚胺类单体与该有机二胺类化合物的摩尔比为(0.5~4):1。
  11. 如权利要求1所述的添加剂，其特征在于，该通过聚合反应得到的聚合物的分子量为1000~500000。
  12. 一种电解质溶液，包括电解质盐、非水溶剂及如权利要求1-11中任意一项所述的添加剂，该非水溶剂包括碳酸丙烯酯。
  13. 如权利要求12所述的电解质溶液，其特征在于，该添加剂在该电解质溶液中的质量体积比浓度为0.01%-10%。
  14. 如权利要求12所述的电解质溶液，其特征在于，该非水溶剂进一步包括碳酸乙烯酯、碳酸二乙酯、碳酸二甲酯、碳酸甲乙酯、碳酸丁烯酯、γ-丁内酯、γ-戊内酯、碳酸二丙酯、N-甲基吡咯烷酮(NMP)、N-甲基甲酰胺、N-甲基乙酰胺、二甲基甲酰胺、二乙基甲酰胺、二乙醚、乙腈、丙腈、苯甲醚、丁二腈、己二腈、戊二腈、二甲亚砜、亚硫酸二甲酯、碳酸亚乙烯酯、碳酸甲乙酯、碳酸二甲酯、碳酸二乙酯、氟代碳酸乙烯酯、氯代碳酸丙烯酯、酸酐、环丁砜、甲氧基甲基砜、四氢呋喃、2-甲基四氢呋喃、环氧丙烷、乙酸甲酯、乙酸乙酯、乙酸丙酯、丁酸甲酯、丙酸乙酯、丙酸甲酯、二甲基甲酰胺、1,3-二氧戊烷、1,2-二乙氧基乙烷、1,2-二甲氧基乙烷、或1,2-二丁氧基中的一种或几种的组合。
  15. 如权利要求12所述的电解质溶液，其特征在于，该电解质盐为LiCl、LiPF6、LiBF4、LiCH3SO3、LiCF3SO3、LiAsF6、LiSbF6、LiClO4、Li[BF2(C2O4)]、Li[PF2(C2O4)2]、Li[N(CF3SO2)2]、Li[C(CF3SO2)3]及LiBOB中的一种或多种。
  16. 一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该电解质溶液包括电解质盐、非水溶剂及如权利要求1-11中任意一项所述的添加剂，该非水溶剂包括碳酸丙烯酯。
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