WO2016066023A1 - 电极粘结剂、正极材料以及锂离子电池 - Google Patents

电极粘结剂、正极材料以及锂离子电池 Download PDF

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WO2016066023A1
WO2016066023A1 PCT/CN2015/091984 CN2015091984W WO2016066023A1 WO 2016066023 A1 WO2016066023 A1 WO 2016066023A1 CN 2015091984 W CN2015091984 W CN 2015091984W WO 2016066023 A1 WO2016066023 A1 WO 2016066023A1
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lithium ion
ion battery
monomer
positive electrode
formula
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PCT/CN2015/091984
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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
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 WO2016066023A1 publication Critical patent/WO2016066023A1/zh
Priority to US15/498,810 priority Critical patent/US20170226291A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
    • 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
    • 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 binder, a positive electrode material, and a lithium ion battery using the same.
  • lithium-ion batteries have the advantages of high energy density, long cycle life, no memory effect and low environmental pollution.
  • lithium battery explosions and injuries in mobile phones and notebook computers have occurred frequently, and the safety of lithium-ion batteries has attracted widespread attention.
  • Lithium-ion batteries emit a large amount of heat in the case of excessive charge and discharge, short circuit, and long-time operation of large currents. Thermal runaway may cause battery burning or explosion, and applications such as electric vehicles have more stringent safety requirements for batteries. . Therefore, the safety research of lithium ion batteries is of great significance.
  • a positive electrode material comprising the above electrode binder.
  • a lithium ion battery comprising a positive electrode, a negative electrode, a separator and an electrolyte solution, the positive electrode comprising the above positive electrode material.
  • the invention reacts a polymer by reacting an organic diamine compound with a dianhydride monomer, and the polymer not only has good viscosity, but also does not affect the normal charge and discharge cycle of the battery in the charging and discharging voltage range of the positive electrode of the lithium ion battery. And can have better thermal stability, and act as an adhesive to protect the positive electrode from overcharge protection.
  • Embodiment 1 is a cycle performance curve of a lithium ion battery according to Embodiment 2 of the present invention.
  • Example 2 is an AC impedance spectrum of a lithium ion battery according to Example 2 of the present invention and Comparative Example 1.
  • FIG 3 is a graph showing changes in voltage and temperature of a battery during overcharge of a lithium ion battery according to Embodiment 6 of the present invention.
  • the electrode binder provided by the present invention, the preparation method thereof, the cathode material and the lithium ion battery using the electrode binder will be further described in detail below with reference to the accompanying drawings and specific embodiments.
  • Embodiments of the present invention provide an electrode binder for a lithium ion battery, 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 electrode binder may have a molecular weight of from 1,000 to 50,000.
  • the present application further provides a method for preparing an 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 allow the reaction to proceed sufficiently to obtain the 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.
  • 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 electrode binder may be further purified. Specifically, the produced polymer solution is washed and dried by a washing reagent to obtain an electrode binder. The catalyst and the reaction solvent are dissolved in the washing reagent, and the 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 positive electrode material comprising a positive electrode active material, a conductive agent, and the above polymer obtained by polymerization of a diamine monomer and a dianhydride monomer as a positive electrode binder.
  • the positive electrode binder can be uniformly mixed with the positive electrode active material and the conductive agent.
  • the positive electrode binder may have a mass percentage of 0.01% to 50%, preferably 1% to 20%, in the positive electrode material.
  • 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 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.
  • An embodiment of the present invention provides a negative electrode material comprising a negative electrode active material, a conductive agent, and the above polymer obtained by polymerization of a diamine monomer and a dianhydride monomer as a negative electrode binder.
  • 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.
  • At least one of the positive electrode and the negative electrode may be a polymer obtained by polymerization of a diamine monomer and a dianhydride monomer as a binder.
  • 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 negative electrode material may be an existing binder, and when the negative electrode material includes when the polymer obtained by polymerization of a diamine monomer and a dianhydride monomer is used as a negative electrode binder, the positive electrode material may be a conventional binder.
  • the existing binder may be in polyvinylidene fluoride (PVDF), polyvinylidene fluoride (PTFE), polytetrafluoroethylene (PTFE), fluorine rubber, EPDM rubber and styrene butadiene rubber (SBR).
  • PVDF polyvinylidene fluoride
  • PTFE polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • fluorine rubber EPDM rubber and styrene butadiene rubber
  • SBR styrene butadiene rubber
  • the positive electrode and the negative electrode may each employ the polymer obtained by polymerization of a diamine monomer and a dianhydride monomer as a binder
  • 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
  • LiNi 1/3 Co 1/3 Mn 1/3 O 2 88% of LiNi 1/3 Co 1/3 Mn 1/3 O 2 , 2% of the positive electrode binder of Example 1 and 10% of conductive graphite were mixed by mass percentage, and dispersed by N-methylpyrrolidone This slurry was applied onto an aluminum foil and vacuum-dried at 120 ° C for 12 hours to prepare a positive electrode tab.
  • the test conditions are: constant current charge and discharge cycle at a current magnification of 0.2 C in the range of 2.8V to 4.3V.
  • FIG. 1 and Table 1 the cycle performance of the first 50 times of the battery of Example 2 is shown in FIG. 1.
  • the retention 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 lithium ion batteries of Example 2 and Comparative Example 1 were charged to a full voltage state of 4.3 V, and an AC impedance spectrum was measured.
  • the frequency range was 100 mHz to 100 kHz, and the amplitude was 5 mV.
  • the impedance of the second embodiment is slightly smaller than that of the comparative example 1.
  • the positive electrode tabs of Example 2 and Comparative Example 1 were weighed first, and then immersed in an electrolytic solution for 48 hours, and then the surface electrolyte was removed by a filter paper and weighed.
  • the conventional PVDF (Comparative Example 1) has no high liquid absorption rate
  • the positive electrode tab of Example 2 can have a certain liquid absorption rate, and can satisfy the requirements of the positive electrode binder for lithium ion battery electrodes.
  • the positive electrode tabs of Example 2 and Comparative Example 1 were subjected to adhesion test. 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 positive 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 positive electrode piece with a pressure roller at a speed of about 300 mm/min under a self-weight, and parked for 20 minutes under the test environment. The test was carried out after 40 minutes.
  • the free end of the positive electrode tab was folded in half by 180o, and the adhesive face was peeled off from the positive electrode tab by 15 mm.
  • the free end of the positive electrode tab 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.
  • the adhesion of Example 2 was superior to that of the conventional PVDF (Comparative Example 1).
  • the lithium ion batteries of Example 6 and Comparative Example 2 were overcharged to 10 V at a current ratio of 1 C, and the phenomenon was observed. Referring to FIG. 3, the maximum temperature during the overcharge process of Embodiment 6 is only 58 °C. Referring to FIG. 4, in the overcharge process of Comparative Example 2, the battery reached a fire temperature of 500 ° C.
  • a polymer obtained by polymerization of a diamine monomer and a dianhydride monomer can be used as a positive electrode binder for a lithium ion battery, and has little influence on a charge and discharge cycle performance of a lithium ion battery, and can be improved.
  • the electrode stability and thermal stability of the lithium ion battery play the role of overcharge protection.

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Abstract

提供了一种锂离子电池电极粘结剂，由包含BAPP（2,2-双[4-(4-氨基苯氧基) 苯基]丙烷）的二胺类单体与二酐类单体通过聚合反应得到。同时还提供了一种正极材料及锂离子电池，该锂离子电池包括正极、负极、隔膜及电解质溶液，该正极材料包括正极活性物质、导电剂及上述粘结剂。

Description

电极粘结剂、正极材料以及锂离子电池 技术领域
本发明涉及一种粘结剂、正极材料及应用该粘结剂的锂离子电池。
背景技术
随着便携式电子产品的快速发展和普遍化，锂离子电池的市场需求与日俱增。与传统二次电池相比，锂离子电池具有能量密度高、循环寿命长、无记忆效应和环境污染小等优点。然而，近年来用于手机、笔记本电脑中的锂电池爆炸伤人事件屡屡发生，锂离子电池的安全问题已引起人们的广泛关注。锂离子电池在过度充放电、短路以及大电流长时间工作的情形下会释放出大量的热，可能发生热失控引起电池燃烧或爆炸，而电动汽车等应用领域对电池有更加严苛的安全要求。因此，锂离子电池的安全性研究具有重要意义。
发明内容
有鉴于此，确有必要提供一种能够提高锂离子电池安全性能的电极粘结剂、正极材料及应用该电极粘结剂的锂离子电池。
一种电极粘结剂，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 WO117-appb-I000001
（1）；
Figure WO117-appb-I000002
（2）；
Figure WO117-appb-I000003
（3）；
Figure WO117-appb-I000004
(4)。
一种正极材料，包括上述电极粘结剂。
一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该正极包括上述正极材料。
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度，在锂离子电池正极充放电电压区间不会影响电池的正常充放电循环，且能够具有较好的热稳定性，在作为粘结剂的同时对正极起到对过充保护的作用。
 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。
图2为本发明实施例2与比较例1的锂离子电池的交流阻抗谱。
图3为本发明实施例6的锂离子电池的过充电时电池的电压及温度随时间变化曲线。
图4为本发明比较例2的锂离子电池的过充电时电池的电压及温度随时间变化曲线。
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极粘结剂及其制备方法、正极材料及应用该电极粘结剂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电极粘结剂，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 WO117-appb-I000005
（1）
Figure WO117-appb-I000006
（2）
Figure WO117-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 WO117-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 WO117-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 WO117-appb-I000010
,
Figure WO117-appb-I000011
,
Figure WO117-appb-I000012
,或
Figure WO117-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。
该电极粘结剂的分子量可以为1000~50000。
本申请进一步提供一种电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，得到该电极粘结剂。
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。
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电极粘结剂提纯，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，得到电极粘结剂。该催化剂及反应溶剂溶于该洗涤试剂，而该电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正极材料，包括正极活性物质、导电剂及上述由二胺类单体与二酐类单体通过聚合反应得到的聚合物作为正极粘结剂。该正极粘结剂可以与该正极活性物质及导电剂均匀混合。该正极粘结剂在该正极材料中的质量百分含量可以为0.01%~50%，优选为1%~20%。
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。
本发明实施方式提供一种负极材料，包括负极活性物质、导电剂及上述由二胺类单体与二酐类单体通过聚合反应得到的聚合物作为负极粘结剂。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。该正极及负极中的至少一方可以采用上述由二胺类单体与二酐类单体通过聚合反应得到的聚合物作为粘结剂。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。
当该正极材料包括所述由二胺类单体与二酐类单体通过聚合反应得到的聚合物作为正极粘结剂时，该负极材料可采用现有的粘结剂，当该负极材料包括所述由二胺类单体与二酐类单体通过聚合反应得到的聚合物作为负极粘结剂时，该正极材料可以采用现有的粘结剂。现有的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。当然，该正极及负极可以均采用所述由二胺类单体与二酐类单体通过聚合反应得到的聚合物作为粘结剂。
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，得到正极粘结剂，为一种纤维状高分子聚合物，由式(6)表示
Figure WO117-appb-I000014
（6）
实施例2
按质量百分比，将85%的LiNi1/3Co1/3Mn1/3O2、5%的实施例1中的正极粘结剂和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极极片。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。
实施例3
按质量百分比，将87%的LiNi1/3Co1/3Mn1/3O2、3%的实施例1中的正极粘结剂和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极极片。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。
实施例4
按质量百分比，将88%的LiNi1/3Co1/3Mn1/3O2、2%的实施例1中的正极粘结剂和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极极片。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。
实施例5
按质量百分比，将88.5%的LiNi1/3Co1/3Mn1/3O2、1.5%的实施例1中的正极粘结剂和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极极片。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。
实施例6
全电池的组装：按质量百分比，将94%的LiNi1/3Co1/3Mn1/3O2、3%的实施例1中的正极粘结剂和3%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铝箔上，于120℃真空干燥，压缩并裁剪制成电池正极。
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%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100℃真空干燥，压缩并裁剪制成电池负极。将正负极匹配，电解液为1M LiPF6 溶于组成为EC/DEC/EMC=1/1/1(v/v/v)的溶剂中，采用卷绕工艺制成63.5mm*51.5mm*4.0mm的软包电池。
比较例1
按质量百分比，将85%的LiNi1/3Co1/3Mn1/3O2、5%的PVDF和10%的导电石墨混合，用N-甲基吡咯烷酮分散，将此浆料涂布于铝箔上，于120℃真空干燥12小时，制成正极极片。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。
比较例2
全电池的组装：按质量百分比，将94%的LiNi1/3Co1/3Mn1/3O2、3%的PVDF和3%的导电石墨混合，用NMP分散，将此浆料涂布于铝箔上，于120℃真空干燥，压缩并裁剪制成电池正极。
按质量百分比，将94%的石墨负极、3.5%的PVDF和2.5%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100℃真空干燥，压缩并裁剪制成电池负极。将正负极匹配，电解液为1M LiPF6, EC/DEC/EMC=1/1/1(v/v/v)，采用卷绕工艺制成63.5mm*51.5mm*4.0mm的软包电池。
电池循环性能测试
测试条件为：在2.8V~4.3V范围内，以0.2C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50次的循环性能如图1所示，实施例2、3、4、5和比较例首次效率、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。
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 86% 144 93%
实施例3 85% 147 94%
实施例4 85% 142 90%
实施例5 84% 138 89%
比较例1 85% 145 93%
阻抗测试
将实施例2与比较例1的锂离子电池充电至4.3V满电态，测交流阻抗谱，频率范围为100mHz~100kHz，振幅为5mV。请参阅图2，实施例2的阻抗比比较例1略小。
吸液率测试
将实施例2和比较例1的正极极片先称重，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的正极极片为12.1%，比较例1的正极极片为15.2%。说明虽然没有传统的PVDF（比较例1）吸液率高，但实施例2的正极极片能够具有一定的吸液率，可以满足在锂离子电池电极正极粘结剂的要求。
粘结力测试
分别对实施例2和比较例1的正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）。一端与正极极片表面粘结，长度100mm，另一端接夹持器，然后用压辊在自重下以约300mm/min的速度在正极极片上来回滚压三次，在试验环境下停放20min~40min后进行试验。将正极极片自由端对折180º，并从正极极片上剥开粘合面15mm。把正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。从表2中可以看出，实施例2的粘结力优于传统的PVDF（比较例1）。
表2
正极极片 试样厚度μm 试样宽度mm 最大负荷N
实施例2 68±2 20 10.3
比较例1 68±2 20 5.5
过充电测试
将实施例6与比较例2的锂离子电池采用1C电流倍率过充至10V，观察现象。请参阅图3，实施例6过充过程中最高温度仅58℃。请参阅图4，对比例2过充过程中电池达到500℃起火燃烧。
本发明实施例采用二胺类单体与二酐类单体通过聚合反应得到的聚合物能够作为正极粘结剂应用于锂离子电池，且对锂离子电池充放电循环性能影响较小，能够提高锂离子电池的电极稳定性及热稳定性，起到过充保护的作用。
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 (11)

  1. 一种锂离子电池电极粘结剂，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 WO117-appb-I000015
    （1）；
    Figure WO117-appb-I000016
    （2）；
    Figure WO117-appb-I000017
    （3）；
    Figure WO117-appb-I000018
    (4)。
  2. 如权利要求1所述的锂离子电池电极粘结剂，其特征在于，R是双酚A基, -O-, -S-, 或-CH2-。
  3. 如权利要求1所述的锂离子电池电极粘结剂，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所述的锂离子电池电极粘结剂，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 WO117-appb-I000019
    (5)。
  5. 如权利要求4所述的锂离子电池电极粘结剂，其特征在于，R4是-(CH2)n-，-O-，-S-， -CH2-O-CH2-，-CH(NH)-(CH2)n-
    Figure WO117-appb-I000020
    ,
    Figure WO117-appb-I000021
    ,
    Figure WO117-appb-I000022
    ,或
    Figure WO117-appb-I000023
    。
  6. 如权利要求4所述的锂离子电池电极粘结剂，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所述的锂离子电池电极粘结剂，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所述的锂离子电池电极粘结剂，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所述的锂离子电池电极粘结剂，其特征在于，该聚合物的分子量为1000~50000。
  10. 一种正极材料，包括如权利要求1-9中任意一项所述的锂离子电池电极粘结剂。
  11. 一种锂离子电池，包括正极、负极、隔膜及电解质溶液，该正极包括如权利要求1-9中任意一项所述的锂离子电池电极粘结剂。
PCT/CN2015/091984 2014-10-29 2015-10-15 电极粘结剂、正极材料以及锂离子电池 WO2016066023A1 (zh)

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