WO2016066024A1 - 负极材料以及应用该负极材料的锂离子电池 - Google Patents

负极材料以及应用该负极材料的锂离子电池 Download PDF

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WO2016066024A1
WO2016066024A1 PCT/CN2015/091991 CN2015091991W WO2016066024A1 WO 2016066024 A1 WO2016066024 A1 WO 2016066024A1 CN 2015091991 W CN2015091991 W CN 2015091991W WO 2016066024 A1 WO2016066024 A1 WO 2016066024A1
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negative electrode
monomer
electrode material
formula
dianhydride
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PCT/CN2015/091991
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English (en)
French (fr)
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钱冠男
何向明
王莉
尚玉明
李建军
罗晶
徐程浩
高剑
王要武
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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 WO2016066024A1 publication Critical patent/WO2016066024A1/zh
Priority to US15/498,837 priority Critical patent/US20170229710A1/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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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
    • H01M2004/027—Negative electrodes
    • 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 negative electrode material containing a novel negative electrode binder and a lithium ion battery using the same.
  • Lithium-ion battery is a new type of green chemical power source. Compared with traditional nickel-cadmium batteries and nickel-hydrogen batteries, it has the advantages of high voltage, long life and high energy density. Since Sony introduced the first generation of lithium-ion batteries in 1990, it has been rapidly developed and widely used in a variety of portable devices.
  • the binder is an important component of the positive and negative electrodes of a lithium ion battery, and is a polymer compound for adhering an electrode active material to a current collector. Its main function is to bond and maintain the electrode active material, and stabilize the pole piece structure to buffer the expansion/contraction of the pole piece during charging and discharging.
  • the binder that can be used in a lithium ion battery needs to be stable in the operating voltage and temperature range of the battery, has a low internal resistance, avoids affecting the normal charge and discharge cycle of the battery, and is insoluble in the battery.
  • Organic solvent for lithium ion battery electrolyte Currently, binders used in lithium ion batteries are mainly organic fluoropolymers such as vinylidene fluoride (PVDF).
  • a negative electrode material comprising a negative electrode binder, wherein the negative electrode binder is a polymer obtained by polymerization of a diamine monomer and a dianhydride monomer, and the dianhydride monomer comprises a formula derived from a molecular formula ( 1) at least one of the monomers represented by the formula (2) and the formula (3), the diamine monomer comprising at least a monomer represented by the formula (4), and R in the formula (3) is a divalent organic Substituent,
  • a lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte solution, the negative electrode comprising the above negative electrode material.
  • the invention passes through an polymerization reaction of an organic diamine compound and a dianhydride monomer, and the polymer not only has good adhesion, but also does not affect the normal charge of the battery in the charging and discharging voltage range of the negative electrode of the lithium ion battery.
  • the discharge cycle can be applied to a negative electrode material of a lithium ion battery as a suitable negative electrode binder.
  • Embodiment 1 is a cycle performance curve of a lithium ion battery according to Embodiment 2 of the present invention.
  • An embodiment of the present invention provides a negative electrode binder which is a polymer obtained by polymerization of a diamine monomer and a dianhydride monomer.
  • the molecular formula of the dianhydride monomer is represented by the formula (1), the formula (2) or the formula (3).
  • R in the formula (3) is a divalent organic substituent, and specifically may be a bisphenol A group, -O-, -S-, -CH 2 -.
  • the dianhydride monomers include, but are not limited to, bisphenol A type diether dianhydride, diphenyl ether tetracarboxylic dianhydride, pyromellitic anhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. One or more of them.
  • the diamine monomer includes at least a monomer represented by the formula (4).
  • the diamine monomer may further include a monomer represented by the formula (5).
  • R 4 is a divalent organic substituent, specifically -(CH 2 ) n -, -O-, -S-, -CH 2 -O-CH 2 -, -CH(NH)-(CH 2 ) n - , , ,or .
  • the molar ratio of the monomer of the formula (4) to the monomer of the formula (5) may be from 1:2 to 10:1, preferably from 1:1 to 3:1.
  • the total molar ratio of the dianhydride monomer to the diamine monomer may be from 1:10 to 10:1, preferably from 1:2 to 4:1.
  • the negative electrode binder may have a molecular weight of 1,000 to 50,000.
  • the present application further provides a method for preparing a negative electrode binder, comprising the steps of polymerizing a dianhydride monomer and the diamine monomer, specifically, the above diamine monomer and dianhydride monomer in an organic solvent. The mixture was mixed, heated and stirred to sufficiently carry out the reaction to obtain the negative electrode binder.
  • the above diamine monomer can be dissolved in an organic solvent to form a diamine solution.
  • the mass ratio of the diamine monomer to the organic solvent in the diamine solution may be 1:100 to 1:1, preferably 1:10 to 1:2.
  • the above dianhydride monomer can be dissolved in an organic solvent to form a dianhydride solution.
  • the mass ratio of the dianhydride monomer to the organic solvent in the dianhydride solution may be 1:100 to 1:1, preferably 1:10 to 1:2.
  • the organic solvent is an organic solvent capable of dissolving the dianhydride monomer and the diamine monomer, such as N,N-dimethylformamide, N,N-dimethylacetamide, propylene carbonate, and N- Methyl pyrrolidone (NMP).
  • One of the dianhydride solution and the diamine solution can be transported to the other by a transfer pump at a certain rate, and the stirring is continued for a certain period of time after the completion of the transfer, so that the reaction proceeds sufficiently.
  • the mixing and stirring time may be from 2 hours to 72 hours, preferably from 12 hours to 24 hours.
  • the reaction temperature of the polymerization reaction may be from 160 ° C to 200 ° C.
  • a catalyst may be further added, and the catalyst may be one or more of benzoic acid, benzenesulfonic acid, phenylacetic acid, pyridine, quinoline, pyrrole, imidazole, and the catalyst is added in an amount of dianhydride. 0.5-5 wt% of the total mass of the body and diamine monomer.
  • the dianhydride monomer and the diamine monomer may be completely dissolved in an organic solvent; then the temperature is raised to 30 ° C to 60 ° C, and the reaction is continuously stirred for 1 hour to 10 hours, preferably 2 hours to 4 hours. Finally, the catalyst is added and the temperature is raised to 160 ° C ⁇ 200 ° C, and the reaction is continuously stirred for 6 hours to 48 hours, preferably 12 hours to 24 hours, to obtain the polymer.
  • the negative electrode binder may be further purified. Specifically, the produced polymer solution is washed and dried by a washing reagent to obtain a negative electrode binder.
  • the catalyst and the reaction solvent are dissolved in the washing reagent, and the negative electrode binder is insoluble in the washing reagent to form a precipitate.
  • the washing reagent may be water, methanol, ethanol, a mixed solution of methanol and water or a mixed solution of ethanol and water (concentration of methanol or ethanol is 5 to 99% by weight).
  • An embodiment of the present invention provides a negative electrode material comprising a negative electrode active material, a conductive agent, and the above negative electrode binder, which is obtained by polymerization of a dianhydride monomer and the diamine monomer.
  • the negative electrode binder can be uniformly mixed with the negative electrode active material and the conductive agent.
  • the negative electrode binder may have a mass percentage in the negative electrode material of 0.01% to 50%, preferably 1% to 20%.
  • the negative electrode active material may be existing, such as at least one of lithium titanate, graphite, phase carbon microspheres (MCMB), acetylene black, microbead carbon, carbon fiber, carbon nanotubes, and cracked carbon.
  • 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 conductive agent may be one of a conventional one, such as a carbon material such as carbon black, a conductive polymer, acetylene black, carbon fiber, carbon nanotube, and graphite.
  • a carbon material such as carbon black, a conductive polymer, acetylene black, carbon fiber, carbon nanotube, and graphite.
  • the embodiment of the invention further provides a lithium ion battery comprising a positive electrode, a negative electrode, a separator and an 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 disposed on a surface of the positive electrode current collector.
  • the negative electrode may further include a negative current collector and a negative electrode material disposed on a surface of the negative current collector. The negative electrode material is opposed to the above positive electrode material and is spaced apart by the separator.
  • the positive electrode material may include a positive electrode active material, and may further include a conductive agent and a positive electrode binder.
  • the positive electrode active material may be at least one of a lithium-transition metal oxide having a layer structure, a lithium-transition metal oxide having a spinel structure, and a lithium-transition metal oxide having an olivine structure, for example, olive. Stone 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 positive electrode binder may be one or more of PVDF, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), fluorine rubber, ethylene propylene diene monomer, and styrene butadiene rubber (SBR).
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • 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. Composite film.
  • the electrolyte solution includes a lithium salt and a non-aqueous solvent.
  • 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 (EC), diethyl carbonate.
  • EC ethylene carbonate
  • Ester (DEC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), 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, dimethyl sulfite, vinylene carbonate, ethyl methyl carbonate, dimethyl carbonate, diethyl carbonate, fluoroethylene carbonate, chlorocarbonate Ester, acid anhydride, sulfolane, methoxymethyl sulfone, tetrahydrofuran, 2-methyltetrahydrofuran, propylene oxide, methyl acetate
  • the lithium salt may include lithium chloride (LiCl), lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium methanesulfonate (LiCH 3 SO 3 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ) Lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluoroantimonate (LiSbF 6 ), lithium perchlorate (LiClO 4 ), Li[BF 2 (C 2 O 4 )], Li[PF 2 (C 2 O) 4 ) one or more of 2 ], Li[N(CF 3 SO 2 ) 2 ], Li[C(CF 3 SO 2 ) 3 ], and lithium bis(oxalate)borate (LiBOB).
  • LiCl lithium chloride
  • LiPF 6 lithium hexafluorophosphate
  • LiBF 4 lithium tetrafluoroborate
  • the test conditions are: a constant current charge and discharge cycle at a current rate of 0.1 C in the range of 0.005 V to 2 V.
  • the cycle performance of the first 70 times of the battery of Example 2 is as shown in FIG. 1.
  • the rate is shown in Table 1. It can be seen that the cycle performance of a lithium ion battery using a polyimide binder is substantially similar to that of a lithium ion battery using a conventional binder PVDF.
  • the faster capacity decline of Comparative Example 2 may be related to a decrease in adhesion.
  • the adhesiveness of the negative electrode binder of the embodiment of the present invention is superior to that of PVDF, so that the capacity retention ratio of the 3% negative electrode binder battery of Example 3 was higher than that of the battery of Comparative Example 2 using the same content of PVDF as a binder.
  • Example 2 and Comparative Example 1 were weighed first, and immersed in an electrolytic solution for 48 hours, and then the surface electrolyte was removed by a filter paper and weighed.
  • the adhesion test of the negative electrode tabs of Example 2 and Comparative Example 1 was carried out, respectively. Use a tape width of 20mm ⁇ 1mm, first remove the outer 3 to 5 layers of adhesive tape, and then take more than 150mm of adhesive tape (adhesive tape bonding surface can not contact hands or other substances). One end is bonded to the surface of the negative electrode piece, the length is 100mm, and the other end is connected to the holder, and then rolled back and forth three times on the negative electrode piece with a pressure roller at a speed of about 300 mm/min under the own weight, and the sample is prepared in the test environment. The test was carried out after parking for 20 min to 40 min.
  • the free end of the negative electrode tab was folded in half by 180o, and the adhesive face was peeled off from the negative electrode tab by 15 mm.
  • the free end of the negative pole piece and the test plate are respectively clamped on the upper and lower holders. Make the peeling surface consistent with the test machine line.
  • the test machine was continuously peeled off at a descending speed of 300 mm/min ⁇ 10 mm/min, and an automatic recorder was used to draw a peeling curve.
  • Negative pole piece Sample thickness ⁇ m Sample width mm Maximum load N
  • Example 2 64 ⁇ 2 20 0.717 Comparative example 1 64 ⁇ 2 20 0.183
  • a polymer is polymerized by an organic diamine compound and a dianhydride monomer, and the polymer not only has good adhesion, but also does not affect the battery in the charging and discharging voltage range of the negative electrode of the lithium ion battery.
  • the normal charge and discharge cycle can be applied to a negative electrode material of a lithium ion battery as a suitable negative electrode binder.

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Abstract

本发明涉及一种负极材料，包括负极粘结剂，该负极粘结剂由二胺类单体与二酐类单体通过聚合反应得到。本发明还涉及一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该负极包括上述负极材料。

Description

负极材料以及应用该负极材料的锂离子电池 技术领域
本发明涉及一种含有新型负极粘结剂的负极材料及应用该负极材料的锂离子电池。
背景技术
锂离子电池是一种新型的绿色化学电源，与传统的镍镉电池、镍氢电池相比具有电压高、寿命长、能量密度大的优点。自1990年日本索尼公司推出第一代锂离子电池后，它已经得到迅速发展并广泛用于各种便携式设备。
粘结剂是锂离子电池正负极的重要组成部分，是一种用于将电极活性物质粘附在集流体上的高分子化合物。其主要作用是粘结和保持电极活性物质，稳定极片结构，以缓冲充放电过程中极片的膨胀/收缩。能够用于锂离子电池的粘结剂除了具有粘结性能外，还需满足在电池的工作电压和温度范围内稳定，具有较低的内阻，避免影响电池的正常充放电循环，且不溶于锂离子电池电解液的有机溶剂。目前，应用于锂离子电池的粘结剂主要是有机氟聚合物，如偏氟乙烯(PVDF)。
发明内容
有鉴于此，确有必要提供一种含有新型负极粘结剂的负极材料及应用该负极材料的锂离子电池。
一种负极材料，包括负极粘结剂，该负极粘结剂是二胺类单体与二酐类单体通过聚合反应得到的聚合物，该二酐类单体包括由分子通式由式(1)、式(2)及式(3)表示的单体中的至少一种，该二胺类单体至少包括由式(4)表示的单体，式（3）中R为二价有机取代基，
Figure WO118-appb-I000001
（1）；
Figure WO118-appb-I000002
（2）；
Figure WO118-appb-I000003
（3）；
Figure WO118-appb-I000004
(4)。
一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该负极包括上述负极材料。
本发明通过有机二胺类化合物与二酐类单体通过聚合反应一种聚合物，该聚合物不但具有较好的粘结力，在锂离子电池负极充放电电压区间不会影响电池的正常充放电循环，能够作为合适的负极粘结剂应用于锂离子电池负极材料。
 附图说明
图1为本发明实施例2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负极材料及应用该负极材料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负极粘结剂，是由二胺类单体与二酐类单体通过聚合反应得到的聚合物。
该二酐类单体的分子通式由式(1)、式(2)或式(3)表示。
Figure WO118-appb-I000005
（1）
Figure WO118-appb-I000006
（2）
Figure WO118-appb-I000007
（3）
式（3）中R为二价有机取代基，具体可以是双酚A基, -O-, -S-, -CH2-。该二酐类单体包括但不局限于双酚A型二醚二酐、二苯醚四甲酸二酐、均苯四甲酸酐及3,3',4,4'-联苯四甲酸二酐中的一种或多种。
该二胺类单体至少包括由式(4)表示的单体。
Figure WO118-appb-I000008
(4)
另外，该二胺类单体还可进一步包括由式(5)表示的单体。
Figure WO118-appb-I000009
(5)
其中R4为二价有机取代基，具体可以是-(CH2)n-，-O-，-S-， -CH2-O-CH2-，-CH(NH)-(CH2)n-
Figure WO118-appb-I000010
,
Figure WO118-appb-I000011
,
Figure WO118-appb-I000012
,或
Figure WO118-appb-I000013
。
其中，式(4)的单体和式(5)的单体的摩尔比可以为1:2~10:1，优选为1:1~3:1。
该二酐类单体与该二胺类单体的总的摩尔比可以为1:10~10:1，优选为1:2~4:1。
该负极粘结剂的分子量可以为1000~50000。
本申请进一步提供一种负极粘结剂的制备方法，包括将二酐类单体与该二胺类单体聚合的步骤，具体是将上述二胺类单体与二酐类单体在有机溶剂中混合、加热并搅拌，使反应充分进行，得到该负极粘结剂。
可以将上述二胺类单体在有机溶剂中溶解形成二胺溶液。该二胺溶液中二胺类单体与有机溶剂的质量比可以为1:100~1:1，优选为1:10~1:2。
可以将上述二酐类单体在有机溶剂中溶解形成二酐溶液。该二酐溶液中二酐类单体与有机溶剂的质量比可以为1:100~1:1，优选为1:10~1:2。
该有机溶剂为能够溶解该二酐类单体与该二胺类单体的有机溶剂，例如N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、碳酸丙烯酯及N-甲基吡咯烷酮(NMP)。
可以通过输送泵以一定速率将二酐溶液与二胺溶液中的一种输送至另一种中，输送完毕后持续搅拌一定时间，使反应充分进行。该混合搅拌的时间可以为2小时~72小时，优选为12小时~24小时。该聚合反应的反应温度可以为160℃~200℃。
在上述聚合反应的过程中可进一步加入催化剂，该催化剂可以为苯甲酸、苯磺酸、苯乙酸、吡啶、喹啉、吡咯、咪唑中的一种或多种，催化剂的加入量为二酐单体与二胺单体总质量的0.5-5wt%。
具体地，可先将二酐类单体与该二胺类单体在有机溶剂中完全溶解；随后升温至30℃~60℃，持续搅拌反应1小时~10小时，优选为2小时~4小时；最后加入催化剂并升温至160℃~200℃，持续搅拌反应6小时~48小时，优选为12小时~24小时，得到所述聚合物。
在反应完毕后可进一步将该负极粘结剂提纯，具体为将生成的聚合物溶液通过一洗涤试剂进行洗涤并烘干，得到负极粘结剂。该催化剂及反应溶剂溶于该洗涤试剂，而该负极粘结剂在该洗涤试剂中不溶，从而形成沉淀。该洗涤试剂可以为水、甲醇、乙醇、甲醇与水的混合溶液或乙醇与水的混合溶液（甲醇或乙醇的浓度为5-99wt%）。
本发明实施方式提供一种负极材料，包括负极活性物质、导电剂及上述负极粘结剂，该负极粘结剂由二酐类单体与该二胺类单体通过聚合反应得到。该负极粘结剂可以与该负极活性物质及导电剂均匀混合。该负极粘结剂在该负极材料中的质量百分含量可以为0.01%~50%，优选为1%~20%。
该负极活性物质可以为现有的，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。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。
该导电剂可以为现有的，如碳素材料，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。
本发明实施例进一步提供一种锂离子电池，包括正极、负极、隔膜及电解质溶液。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设置在该正极集流体表面的正极材料。所述负极可进一步包括一负极集流体及设置在该负极集流体表面的负极材料。该负极材料与上述正极材料相对且通过所述隔膜间隔设置。
该正极材料可包括正极活性物质，并可进一步包括导电剂及正极粘结剂。该正极活性物质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。
该正极粘结剂可以是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。
该电解质溶液包括锂盐及非水溶剂。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（EC）、碳酸二乙酯（DEC）、碳酸丙烯酯（PC）、碳酸二甲酯（DMC）、碳酸甲乙酯（EMC）、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。
该锂盐可包括氯化锂（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。
实施例1
按摩尔比，在三口烧瓶中加入0.4份2,2'-双(4-氨基苯氧基苯基)丙烷（BAPP），0.6份4,4’-二氨基二苯醚(ODA)，有机溶剂间甲酚（溶液固含量约10%），室温搅拌，待完全溶解后，加入1份二苯醚四甲酸二酐，完全溶解后，升温至50℃，反应4小时，加入催化剂苯甲酸1.5ml，升温至180℃，反应24小时，终止反应，在甲醇中沉淀，得到负极粘结剂，为一种纤维状高分子聚合物，由式(6)表示
Figure WO118-appb-I000014
（6）
实施例2
按质量百分比，将85%的石墨负极、5%的实施例1中的负极粘结剂和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铜箔上，于120℃真空干燥12小时，制成负极极片。以锂片作为对电极，电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中，组装成2032扣式电池，进行充放电性能测试。
实施例3
按质量百分比，将87%的石墨负极、3%的实施例1中的负极粘结剂和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铜箔上，于120℃真空干燥12小时，制成负极极片。以锂片作为对电极，电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中，组装成2032扣式电池，进行充放电性能测试。
比较例1
按质量百分比，将85%的负极石墨、5%的PVDF和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铜箔上，于120℃真空干燥12小时，制成负极极片。以锂片作为对电极，电解液为EC/DEC/EMC=1/1/1 1M LiPF6，组装成2032扣式电池，进行充放电性能测试。
比较例2
按质量百分比，将87%的负极石墨、3%的PVDF和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铜箔上，于120℃真空干燥12小时，制成负极极片。以锂片作为对电极，电解液为EC/DEC/EMC=1/1/1 1M LiPF6，组装成2032扣式电池，进行充放电性能测试。
电池循环性能测试
测试条件为：在0.005V~2V范围内，以0.1C的电流倍率恒流充放电循环。请参阅图1及表1，实施例2电池前70次的循环性能如图1所示，实施例2、3和比较例1、2首次效率、第100次放电比容量及第100次容量保持率如表1所示。可以看到采用聚酰亚胺粘结剂的锂离子电池循环性能与采用传统粘结剂PVDF的锂离子电池的循环性能基本相似，比较例2容量衰退较快可能与粘结力降低有关，而本发明实施例的负极粘结剂的粘结力优于PVDF，因此实施例3含有3%负极粘结剂电池的容量保持率比比较例2采用相同含量的PVDF作为粘结剂的电池高。
表1
首次效率（%） 第100次循环比容量（mAh/g） 第100次容量保持率（%）
实施例2 70 333 91
实施例3 73 330 90
比较例1 87 332 95
比较例2 79 286 84
吸液率测试
将实施例2和比较例1的负极极片先称重，放入电解液中浸泡48小时后，取出用滤纸擦干表面电解液，称重。计算公式(浸泡后的极片质量-浸泡前的极片质量)/浸泡前的极片质量*100%的值，实施例2的负极极片为34.5%，比较例1的负极极片为21.0%。
粘结力测试
分别对实施例2和比较例1的负极极片进行粘结力测试。使用的胶粘带宽度为20mm±1mm，先撕去外面的3～5层的胶粘带，然后再取150mm以上的胶粘带（胶粘带粘合面不能接触手或其他物质）。一端与负极极片表面粘结，长度100mm，另一端接夹持器，然后用压辊在自重下以约300mm/min的速度在负极极片上来回滚压三次，试样制备后在试验环境下停放20min~40min后进行试验。将负极极片自由端对折180º，并从负极极片上剥开粘合面15mm。把负极极片自由端和试验板分别夹在上、下夹持器上。使剥离面与试验机力线保持一致。试验机以300mm/min±10mm/min下降速度连续剥离，并有自动记录仪绘出剥离曲线。
表2
负极极片 试样厚度μm 试样宽度mm 最大负荷N
实施例2 64±2 20 0.717
比较例1 64±2 20 0.183
本发明实施例通过有机二胺类化合物与二酐类单体通过聚合反应一种聚合物，该聚合物不但具有较好的粘结力，在锂离子电池负极充放电电压区间不会影响电池的正常充放电循环，能够作为合适的负极粘结剂应用于锂离子电池负极材料。
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 (10)

  1. 一种负极材料，包括负极粘结剂，该负极粘结剂是由二胺类单体与二酐类单体通过聚合反应得到的聚合物，该二酐类单体包括由分子通式由式(1)、式(2)及式(3)表示的单体中的至少一种，该二胺类单体至少包括由式(4)表示的单体，式（3）中R为二价有机取代基，
    Figure WO118-appb-I000015
    （1）；
    Figure WO118-appb-I000016
    （2）；
    Figure WO118-appb-I000017
    （3）；
    Figure WO118-appb-I000018
    (4)。
  2. 如权利要求1所述的负极材料，其特征在于，R是双酚A基, -O-, -S-, 或-CH2-。
  3. 如权利要求1所述的负极材料，其特征在于，该二酐类单体包括双酚A型二醚二酐、二苯醚四甲酸二酐、均苯四甲酸酐及3,3',4,4'-联苯四甲酸二酐中的一种或多种。
  4. 如权利要求1所述的负极材料，其特征在于，该二胺类单体进一步包括由式(5)表示的单体，其中R4为二价有机取代基，
    Figure WO118-appb-I000019
    (5)。
  5. 如权利要求4所述的负极材料，其特征在于，R4是-(CH2)n-，-O-，-S-， -CH2-O-CH2-，-CH(NH)-(CH2)n-
    Figure WO118-appb-I000020
    ,
    Figure WO118-appb-I000021
    ,
    Figure WO118-appb-I000022
    ,或
    Figure WO118-appb-I000023
    。
  6. 如权利要求4所述的负极材料，其特征在于，所述式(4)的单体和式(5)的单体的摩尔比为1:2~10:1。
  7. 如权利要求4所述的负极材料，其特征在于，所述式(4)的单体和式(5)的单体的摩尔比为1:1~3:1。
  8. 如权利要求1所述的负极材料，其特征在于，该二酐类单体与该二胺类单体的摩尔比为1:2~4:1。
  9. 如权利要求1所述的负极材料，其特征在于，该聚合物的分子量为1000~50000。
  10. 一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该负极包括如权利要求1-9中任意一项所述的负极材料。
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