WO2018195897A1 - 用于锂离子电池的复合粘结剂及其制备方法 - Google Patents

用于锂离子电池的复合粘结剂及其制备方法 Download PDF

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WO2018195897A1
WO2018195897A1 PCT/CN2017/082375 CN2017082375W WO2018195897A1 WO 2018195897 A1 WO2018195897 A1 WO 2018195897A1 CN 2017082375 W CN2017082375 W CN 2017082375W WO 2018195897 A1 WO2018195897 A1 WO 2018195897A1
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binder
composite binder
composite
paa
structural formula
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French (fr)
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杨军
别依田
张晶晶
窦玉倩
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罗伯特·博世有限公司
杨军
别依田
张晶晶
窦玉倩
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Priority to CN201780089901.4A priority Critical patent/CN110573544B/zh
Priority to PCT/CN2017/082375 priority patent/WO2018195897A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • 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
    • 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

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  • This invention relates to the field of batteries and, in particular, to the development and improvement of composite binders useful as silicon-containing anode materials for lithium ion batteries.
  • graphite as a form of carbon is an important negative electrode material for lithium ion batteries commonly used in mobile phones, notebook computers, digital cameras, power tools, and the like.
  • the lower theoretical lithium storage capacity (372 mAh/g) of the graphite electrode itself makes it difficult to make breakthroughs. Therefore, research and development of new anode materials with high specific capacity, high charge and discharge efficiency, high cycle performance, high rate charge and discharge performance, high safety and low cost is extremely urgent, and has become a research field in lithium ion batteries. Hot topics are of great significance for the future development of lithium-ion batteries.
  • volume expansion rate >300%) the process of highly intercalating and deintercalating lithium, there is a very significant volume expansion (volume expansion rate >300%), and the resulting mechanical stress causes the electrode material to gradually pulverize during the cycle, and the material structure is destroyed. Loss of electrical contact between the active materials results in a decrease in cycle performance. The above reasons limit the commercial application of silicon-based materials.
  • a binder suitable for a silicon negative electrode plays an important role in maintaining the integrity of the electrode during electrode volume change.
  • a binder containing a carboxyl group such as polyacrylic acid (PAA), carboxymethylcellulose (CMC), sodium alginate (SA) or the like is often used because a carboxyl group on such a binder can form a hydrogen bond with silicon.
  • One of the objects of the present invention is to provide an improvement in a composite binder for a silicon-containing electrode for a lithium ion battery.
  • Another object of the present invention is to enable lithium ion batteries to achieve excellent cycle stability and high coulombic efficiency by improving the binder.
  • the present inventors have unexpectedly found that when a polymer represented by the following structural formula I is introduced into a carboxyl group-containing binder of a silicon-containing negative electrode, cycle stability and coulombic efficiency of a lithium ion battery including the silicon-containing negative electrode can be remarkably improved.
  • R is -CH 3 or -H
  • z is an integer of 0-6, preferably z is an integer between 0-3, more preferably z is an integer between 0-2, and the polymer represented by Structural Formula I has a number average molecular weight of 200,000-500,000.
  • a composite binder comprising a carboxyl group-containing binder and a polymer represented by Structural Formula I.
  • a gel-like substance can be formed in an organic solvent such as N-methylpyrrolidone by physically mixing a carboxyl group-containing binder and a polymer represented by the formula I.
  • a carboxyl group-containing binder herein, polyacrylic acid (hereafter referred to as PAA) is exemplified
  • PAA polyacrylic acid
  • Structural Formula I poly(dopamine methacryl)
  • p(DMA-co-MEA) The amide-co-methoxyethyl acrylate
  • the methoxyethyl acrylate (hereafter referred to as MEA) unit contains a CO bond, thereby making the polymer elastic, while dopamine methacrylamide (hereafter, referred to as The DMA) unit contains a phenolic hydroxyl group capable of forming a hydrogen bond with the MEA, making the polymer sticky.
  • the polymer can also crosslink with a carboxyl group-containing binder such as a carboxyl group of PAA to form both a hydrogen bond and a covalent bond.
  • the binder contains both carboxyl and hydroxyl functional groups and thus can be tightly bonded to the Si particles, exhibiting a high bonding mechanical strength on Si and a particularly recoverable deformation by reversible morphological changes with the Si particles.
  • the present invention also provides a method for preparing a composite binder comprising radically copolymerizing a dopamine methacrylamide monomer with a monomer represented by Structural Formula II;
  • R is -CH 3 or -H
  • z is an integer from 0 to 6, preferably z is an integer between 0 and 3, more preferably z is an integer between 0 and 2
  • dopamine methacrylamide is a single
  • the molar ratio of the body to the monomer represented by Structural Formula II is in the range of 1:1 to 1:20, preferably 1:5 to 1:18, more preferably 1:7.5 to 1:15;
  • the monomer represented by Structural Formula 2 may be, for example, a methoxyethyl acrylate monomer or a 2-hydroxyethyl acrylate monomer.
  • the present invention also provides an electrode material comprising the above composite binder and a lithium ion battery.
  • FIG. 2 is a view showing lithium ions in a lithium ion battery in which a composite binder according to Examples 1 to 4 of the present invention and a binder of Comparative Examples 1 to 3 are respectively used for a negative electrode including silicon-graphite as a negative electrode active material. a diagram of the electrochemical performance of the battery;
  • FIG. 3 is a graph showing the cycle performance of a composite binder of Examples 2, 5, and 6 according to the present invention and a binder of Comparative Example 1 for use in a lithium ion battery including a cathode of silicon-graphite as a negative electrode active material, respectively.
  • FIG. 4 is a graph showing an extended cycle performance in a lithium ion battery using a composite binder A2 (PAA-c-P2) of Example 2 of the present invention in a negative electrode including silicon-graphite as a negative electrode active material;
  • PAA-c-P2 composite binder A2
  • FIG. 5 is a view showing a composite binder A2 (PAA-c-P2) according to Example 2 of the present invention and a PAA binder of Comparative Example 1 in a lithium ion battery for a negative electrode containing only silicon as a negative electrode active material, respectively. , a diagram of the electrochemical performance of a lithium ion battery;
  • FIG. 6 is a graph showing the electrochemical performance of a lithium ion battery when the composite binder A7 according to Example 7 of the present invention is used in a lithium ion battery including a cathode of silicon-graphite as a negative electrode active material.
  • compositions,comprising comprising,comprising, “includes”, “has,having” or “contains,containing” or any other variant thereof as used herein are intended to cover Non-exclusive inclusion.
  • a composition, process, method, article, or device that comprises a plurality of elements is not limited to only those elements, but may also include other elements not specifically recited or inherent to such compositions, processes, methods, articles, or devices.
  • the conjunction “consisting of” does not include any element, step, or ingredient that is not specifically recited.
  • the present inventors have unexpectedly found that when a polymer represented by Structural Formula I is introduced into a carboxyl group-containing binder of a silicon-containing negative electrode, cycle stability and coulombic efficiency of a lithium ion battery including the silicon-containing negative electrode can be remarkably improved. Without being bound by theory, it is believed that this improvement is due to the synergy between the different components of the binder and the strong chemical bonding to the silicon particles.
  • p(DME-co-MEA) has better elasticity and viscosity.
  • MEA includes a large number of CO bonds, which makes the polymer elastic, and after undergoing huge volume expansion, deformation can be restored.
  • the DMA contains a phenolic hydroxyl group to form a hydrogen bond with the MEA, making the polymer sticky. In addition, it contributes to the formation of a stable SEI layer of a silicon negative electrode.
  • the novel interpenetrating gel binder has great potential as a high-capacity silicon anode in next-generation lithium-ion batteries, and can also be used as a convenient solution preparation method and eco-friendly and low-cost factors. Other electrode materials that need to undergo large volume changes.
  • the carboxyl group-containing binder includes polyacrylic acid, carboxymethylcellulose, alginic acid, and polysaccharides, and the polysaccharide includes oxidized starch, carrageenan, xanthan gum, and the like.
  • the carboxyl group-containing binder is polyacrylic acid.
  • the composite binder comprises a mixture of PAA and poly(dopamine methacrylamide-co-methoxyethyl acrylate) (abbreviated as p(DMA-co-MEA)), wherein PAA
  • the weight ratio to p(DMA-co-MEA) is in the range of from 0.1:1 to 10:1, preferably in the range of from 0.5:1 to 7:1, more preferably in the range of from 1:1 to 4:1.
  • poly(dopamine methacrylamide-co-methoxyethyl acrylate) consists of methoxyethyl acrylate (MEA) and dopamine A Copolymerization of acrylamide (DMA), wherein the molar ratio of dopamine methacrylamide to methoxyethyl acrylate is in the range of 1:1 to 1:20, preferably in the range of 1:5 to 1:18, A range of 1:7.5 to 1:15 is preferred.
  • a novel gel-like binder formed by mixing PAA and p (DMA-co-MEA) is designed and synthesized.
  • the volume change during charge and discharge can be effectively suppressed by this elastic binder.
  • the binder coexists with hydrogen bonds by crosslinking and forming covalent bonds to exhibit high mechanical strength bonding on Si and a special 3D network.
  • the modified binder can effectively accommodate the huge volume change of the Si anode in the lithium insertion/delithiation process while maintaining better cycle stability and higher coulomb. Efficiency, even at high current densities and high loads.
  • the battery using the modified binder has better cycle performance than the PAA binder.
  • the present invention using the modified binder achieves a capacity retention rate of up to 91% over 200 cycles compared to a capacity retention of less than 60% using a PAA binder.
  • the battery performance using the modified binder is also superior to those using the PAA binder.
  • the present invention also tests the C-rate performance of a silicon-graphite composite negative electrode and a silicon negative electrode using a different binder in a lithium battery. B-rate performance of batteries using the modified binder has been demonstrated to be superior to those using PAA binders.
  • Another advantage of the present invention is that the synthesis method is easy to implement and easy to scale up.
  • MEA methoxyethyl acrylate, commercially available from Acros, 98%) was passed through a column packed with 30 g of Al 2 O 3 to remove the polymerization inhibitor.
  • the solution mixture was degassed three times by pump-freeze-thaw. When sealed under vacuum, the solution was heated to 60 ° C and stirred overnight.
  • the reaction mixture was diluted with 5 ml of methanol and added to 400 ml of Et 2 O to precipitate a polymer. After reprecipitation twice in DCM/Et 2 O and dried in a vacuum drier, 5.7 g of a white viscous solid polymer was obtained.
  • the polymer P1 prepared above was mixed with PAA (Sigma Aldrich) at a weight ratio of P1 to PAA of 1:4 in an NMP solution to form a composite binder A1 of the inventive example 1 (also denoted as PAA- c-P1).
  • PAA Sigma Aldrich
  • a composite binder A2 according to the present invention (also referred to as PAA-c-P2) was prepared in the same manner as in Example 1 except that P2 was obtained by polymerization of DMA and MEA in different ratios as shown in Table 1. ).
  • a composite binder A3 according to the present invention (also referred to as PAA-c-P3) was prepared in the same manner as in Example 1, except that P3 was obtained by polymerization of DMA and MEA in different ratios as shown in Table 1. ).
  • a composite binder A4 according to the present invention (also referred to as PAA-c-P4) was prepared in the same manner as in Example 1, except that P4 was obtained by polymerization of different ratios of DMA and MEA as shown in Table 1. ).
  • the polymer P2 prepared above was mixed with PAA (Sigma Aldrich) in a weight ratio of P2 to PAA of 1:2 in an NMP solution to form a composite binder A5 of the present invention.
  • PAA Sigma Aldrich
  • the polymer P2 prepared above was mixed with PAA (Sigma Aldrich) in a weight ratio of P2 to PAA of 1:1 in an NMP solution to form a composite binder A6 of the present invention.
  • PAA Sigma Aldrich
  • HEA 77 mmol, 2-hydroxyethyl acrylate, commercially available from Acros, 98%)
  • 1.7 g of the DMA (7.7 mmol) prepared above and 106 g of azobisisobutyronitrile (0.64 mmol) were added to In 20 ml of DMF in an airtight flask.
  • the solution mixture was degassed three times by pump-freeze-thaw. When sealed under vacuum, the solution was heated to 60 ° C and stirred overnight.
  • the reaction mixture was diluted with 5 ml of methanol and added to 400 ml of Et 2 O to precipitate a polymer.
  • the polymer P5 prepared above was mixed with PAA (Sigma Aldrich) at a weight ratio of P5 to PAA of 1:4 in an NMP solution to form a composite binder A7 of Example 7 of the present invention.
  • PAA Sigma Aldrich
  • PAA poly(acrylic acid)
  • PAA-c-p PAA-c-p
  • p(MEA) was synthesized by dissolving 5 g of purified MEA monomer in 20 mL of DMF, adding AIBN 60 mg, transferring it to a flask, and degassing the solution mixture three times by pump-freeze-thaw. When sealed under vacuum, the solution was heated to 60 ° C and stirred overnight. The reaction mixture was diluted with 5 ml of methanol and added to 400 ml of Et 2 O to precipitate a polymer. After reprecipitation twice in DCM/Et 2 O and dried in a vacuum drier, 4.0 g of a colorless, transparent, viscous solid polymer was obtained. The polymer was dissolved in methanol and dialyzed against methanol using a dialysis membrane having a molecular weight cut-off of 12-14 kDa.
  • PAA-c-p DMA
  • p(DMA) was synthesized as follows: 2 g of DMA monomer powder was dissolved in 10 mL of DMF, 30 mg of AIBN was added, transferred to a flask, and the solution mixture was degassed three times by a pump-freeze-thaw cycle. When sealed under vacuum, the solution was heated to 60 ° C and stirred overnight. The reaction mixture was diluted with 5 ml of methanol and added to 400 ml of Et 2 O to precipitate a polymer. After reprecipitation twice in DCM/Et 2 O and dried in a vacuum drier, 1.2 g of a gray viscous solid polymer was obtained. The polymer was dissolved in methanol and dialyzed against methanol using a dialysis membrane having a molecular weight cut-off of 12-14 kDa.
  • the active material Si powder Alfa Aesar
  • graphite graphite
  • carbon black conductive agent Super P 40 nm, Timical
  • the composite binder prepared above were mixed at a weight ratio of 35:45:7:13, uniformly stirred and then applied.
  • the electrode was then dried, cut into a 12 mm diameter disk, pressed at 3 MPa, and finally the silicon electrode was heat treated at 70 ° C for 5 hours, and then heated to 150 ° C under vacuum for 4 hours.
  • the active material Si powder Alfa Aesar
  • the carbon black conductive agent Super P 40 nm, Timical
  • the composite binder prepared above are mixed at a weight ratio of 6:2:2 or 8:1:1, respectively, and stirred uniformly. It was applied to a Cu foil, after which the electrode was dried, cut into a 12 mm diameter disk, pressed at 3 MPa, and finally the silicon electrode was heat treated at 70 ° C for 5 hours, and then heated to 150 ° C under vacuum for 4 hours.
  • the CR2016 button battery was assembled in an argon-filled glove box (MB-10 compact, MBraun) using 1 M in a 1:1 volume ratio mixed solvent of dimethyl carbonate (DMC) and ethylene carbonate (EC).
  • LiPF 6 includes 10% by weight of fluoroethylene carbonate (FEC) as an electrolyte, and a PE film (Celgard 2400) as a separator and lithium metal as a counter electrode.
  • the cutoff voltage is 1.2 V (vs. Li + /Li).
  • the specific capacity is calculated based on the weight of the Si-graphite composite or Si.
  • the weight load of the active material in each electrode was as follows: when silicon-graphite was used as the negative electrode active material, the loading amount was 2 mg/cm 2 , and when only silicon was used as the negative electrode active material, the loading amount was 0.8 mg. /cm 2 .
  • FIG. 2 shows the electrochemical performance of a silicon-graphite-containing negative electrode when the composite binder of Examples 1-4 and the binder of Comparative Examples 1-3 were used in a lithium ion battery, respectively.
  • Figures 2(a) and (b) show the use of the composite binders of Examples 1-4 and Comparative Examples 1-3, respectively, at 1C (after two cycles of 0.2 C and 0.5 C, respectively).
  • the negative conductivity of the silicon-graphite-containing anode of the binder is shown in FIG. 1C (after two cycles of 0.2 C and 0.5 C, respectively.
  • Figure 2(b) shows the cycle performance of a composite containing a composite binder A2 of Example 2 and a silicon-graphite-containing anode each using PAA, PAA-cp (MEA) and PAA-cp (DMA) as binders, respectively.
  • PAA-cp (MEA) refers to a mixture of PAA and polymethoxyethyl acrylate
  • PAA-cp (DMA) refers to a mixture of PAA and polydopamine methacrylamide.
  • Fig. 2(c) shows the C-rate performance of a silicon-graphite-containing negative electrode using PAA and A2 (PAA-c-P2) of Example 2 of the present invention as a binder, respectively.
  • Figure 2(d) shows the use of PAA and A2 (PAA-c-P2) of Example 2 of the present invention as a bond at 200 cycles in 1C (after two cycles of 0.2 C and 0.5 C, respectively).
  • the cycle performance of the silicon-graphite-containing anode of the agent As can be seen from the above figure, the silicon-graphite-containing anode using the A2 of Example 2 as a composite binder The magnification and cycle performance are significantly improved compared to the use of PAA as a binder.
  • the batteries prepared by using the composite binder of Examples 1 to 4 of the present invention can obtain excellent cycle performance.
  • Figure 3 is a graph showing the cycle performance of PAA and P2 polymers (composite binders in Examples 2, 5 and 6) as composite binders in a lithium ion battery containing a negative electrode of silicon-graphite in different weight ratios. . As can be seen from the figure, when the weight ratio of PAA to P2 is 4:1, the electrochemical performance is optimal.
  • FIG. 4 shows the use of A2 (PAA-c-P2) of Example 2 of the present invention as a binder at 1 C (0.2 C and 0.5 C, respectively).
  • A2 PAA-c-P2
  • Example 2 of the present invention Extended cycle performance of a silicon-graphite negative lithium-ion battery with 1000 cycles after two cycles.
  • the composite binder A2 of the embodiment 2 of the present invention when used, the battery can maintain a capacity of 91% after 200 turns and maintain a capacity of 80% after 500 cycles, even at 1000 cycles. It can still maintain a capacity higher than 50%.
  • the present invention further investigates the performance of the composite binder of the present invention in a battery of an anode active material composed only of silicon.
  • the carbon black conductive agent Super P 40 nm, Timical
  • the prepared binder 6:2:2, 8:1:1, respectively, and Example 1
  • the electrode was prepared in the same manner as -4 and assembled into a battery.
  • Figure 5 shows the electrochemical performance of a lithium ion battery using a silicon negative electrode using PAA and A2 (PAA-c-P2) of Example 2 of the present invention as a composite binder.
  • PAA-c-P2 PAA-c-P2
  • Figure 5 shows the electrochemical performance of a lithium ion battery using a silicon negative electrode using PAA and A2 (PAA-c-P2) of Example 2 of the present invention as a composite binder.
  • PAA-c-P2 PAA and A2
  • Fig. 6 shows the electrochemical performance of a lithium ion battery using a silicon negative electrode of A7 of the present invention as a composite binder. As can be seen from the figure, the cycle performance of the silicon-graphite-containing anode using the composite binder was significantly improved.

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Abstract

本发明公开了用于锂离子电池的新型粘结剂、包含该粘结剂的电极材料和锂离子电池，以及所述粘结剂的制备方法，所述粘结剂包含含羧基的粘结剂和由结构式I表示的聚合物的混合物。

Description

用于锂离子电池的复合粘结剂及其制备方法 技术领域
本发明涉及电池领域，具体而言，涉及可用作锂离子电池的含硅负极材料的复合粘结剂的开发和改善。
背景技术
目前石墨作为一种碳的形式是通常用于手机、笔记本电脑、数码相机、电动工具等的锂离子电池的重要负极材料。但是，石墨电极本身较低的理论储锂容量(372mAh/g)使其很难再取得突破性进展。因此，研究和开发具有高比容量、高充放电效率、高循环性能、高倍率充放电性能好、高安全性以及低成本的新型负极材料极具紧迫性，已成为锂离子电池研究领域中的热门课题，并对锂离子电池的日后发展具有十分重要的意义。
硅因其具有最高的理论储锂容量(4200mAh/g)、嵌锂电位低(低于0.5V vs Li/Li+)、电解液反应活性低、自然界储量丰富、价格低廉等优点而备受瞩目。然而，硅基材料在高度嵌脱锂过程中，存在非常显著的体积膨胀(体积膨胀率＞300％)，由此产生的机械应力使电极材料在循环过程中逐渐粉化，材料结构被破坏，活性物质之间电接触丧失，导致循环性能下降。上述原因限制了硅基材料的商业化应用。
提高硅负极性能的措施之一是研发适于硅负极的粘结剂，研究表明粘结剂网络在电极体积变化期间对于维持电极的整体性具有重要作用。包含羧基的粘结剂，例如聚丙烯酸(PAA)、羧甲基纤维素(CMC)、海藻酸钠(SA)等经常被使用，因为这种粘结剂上的羧基能够与硅形成氢键。
然而，由羧基形成的氢键仍不足以克服硅的体积变化，特别是在高质量负载的情况下。
发明内容
本发明的目的之一是提供对用于锂离子电池的含硅电极的复合粘结剂的改进。
本发明的另一目的是通过改进粘结剂，使锂离子电池可实现优异的循环稳定性和高的库仑效率。
本发明人出人意料地发现当在含硅负极的含羧基的粘结剂中引入由如下结构式I表示的聚合物时，可以显著改善包含该含硅负极的锂离子电池的循环稳定性和库仑效率。
Figure PCTCN2017082375-appb-000001
其中，R为-CH3或-H，x∶y＝3∶1-16∶1，优选x∶y＝5∶1-12∶1，更优选x∶y＝6∶1-10∶1，z为0-6的整数，优选z为0-3之间的整数，更优选z为0-2之间的整数，并且由结构式I所表示的聚合物的数均分子量为200,000-500,000。
本发明的上述目的通过如下的复合粘结剂实现，所述复合粘结剂包含含羧基的粘结剂和由结构式I表示的聚合物。根据本发明，通过物理混合含羧基的粘结剂和由结构式I表示的聚合物可以在有机溶剂如N-甲基吡咯烷酮中形成凝胶状物质。
不受理论的约束，据信含羧基的粘结剂(在此以聚丙烯酸(在此及后简称为PAA)为例)与由结构式I表示的聚合物(在此以聚(多巴胺甲基丙烯酰胺-共-丙烯酸甲氧基乙酯)简写为“p(DMA-co-MEA)”为例)可以形成如下式III所示的共价键和氢键键合：
Figure PCTCN2017082375-appb-000002
由上述式III可看出，丙烯酸甲氧基乙酯(在此及后，简称为MEA)单元包含C-O键，从而使得聚合物具有弹性，同时多巴胺甲基丙烯酰胺(在此及后，简称为DMA)单元含有酚羟基，能够与MEA形成氢键，使得聚合物具有粘性。并且，该聚合物与含羧基的粘结剂例如PAA的羧基之间也能交联而既形成氢键又形成共价键。该粘结剂同时包含羧基和羟基官能团，因此可以与Si颗粒紧密地键合，通过与Si颗粒可逆的形态改变，显示在Si上高的键合机械强度以及特别地可恢复的形变。
在本发明中，优选由结构式I表示的聚合物为聚(多巴胺甲基丙烯酰胺-共-丙烯酸甲氧基乙酯)，也简写为p(DMA-co-MEA)，其中z＝0，R为-CH3。或者，也优选由结构式I表示的聚合物为聚(多巴胺甲基丙烯酰胺-共-丙烯酸-2-羟乙酯)，也简称为“p(DMA-co-HEA)”，其中z＝0，R为-H。
为了清楚起见，以下具体描述了MEA、DMA、p(MEA)、p(DMA)、p(DMA-co-MEA)和p(DMA-co-HEA)的分子结构式。
Figure PCTCN2017082375-appb-000003
本发明还提供复合粘结剂的制备方法，其包括将多巴胺甲基丙烯酰胺单体与由结构式II表示的单体进行自由基共聚；
Figure PCTCN2017082375-appb-000004
其中，R为-CH3或-H，z为0-6的整数，优选z为0-3之间的整数，更优选z为0-2之间的整数，并且，多巴胺甲基丙烯酰胺单体与由结构式II表示的单体的摩尔比在1∶1至1∶20，优选1∶5至1∶18，更优选1∶7.5至1∶15的范围；和
(2)将含羧基的粘结剂与步骤(1)中获得的共聚物进行物理混合。
具体地说，由结构式2表示的单体可以是例如丙烯酸甲氧基乙酯单体或丙烯酸-2-羟乙酯单体。
相应地，本发明还提供包含上述复合粘结剂的电极材料和锂离子电池。
附图说明
图1是根据本发明的实施例4合成的P4“聚(多巴胺甲基丙烯酰胺-共-丙烯酸甲氧基乙酯)”的核磁图谱；其中该p(DMA-co-MEA)的分子量为350000，x∶y＝12∶1。
图2是显示根据本发明的实施例1-4的复合粘结剂和对比例1-3的粘结剂分别用于包含硅-石墨作为负极活性材料的负极的锂离子电池中时，锂离子电池的电化学性能的图；
图3是显示根据本发明的实施例2、5和6的复合粘结剂和对比例1的粘结剂分别用于包含硅-石墨作为负极活性材料的负极的锂离子电池中的循环性能的图；
图4是显示使用本发明的实施例2的复合粘结剂A2(PAA-c-P2)在包含硅-石墨作为负极活性材料的负极的锂离子电池中的延长的循环性能的图；
图5是显示根据本发明实施例2的复合粘结剂A2(PAA-c-P2)和对比例1的PAA粘结剂分别用于仅包含硅作为负极活性材料的负极的锂离子电池中时，锂离子电池的电化学性能的图；
图6是显示根据本发明的实施例7的复合粘结剂A7用于包含硅-石墨作为负极活性材料的负极的锂离子电池中时，锂离子电池的电化学性能的图。
具体实施方式
除非另外说明，本文所提及的所有出版物、专利申请、专利和其他参考文献通过引用明确地将其全部内容加入本文中，如同将它们在本文中被全公开。
除非另有限定，此处所用的所有科技术语具有与本发明所属领域技术人员通常理解的相同的含义。在抵触情况下，则以本说明书的定义为准。
除非另有指示，全部的百分比、份数、比率等是按重量计的。
本文中所用的术语“包含(comprises，comprising)”、“包括(includes，including)”、“具有(has，having)”或“含有(contains，containing)”或其任何其它的变体旨在覆盖非排除性的包含。例如，包含一系列要素的组合物、工艺、方法、制品或设备不仅仅局限于这些要素，而且还可以包括这些组合物、工艺、方法、制品或设备所未明确列举的或所固有的其它要素。连接词“由...组成”不包括任何没有明确列举的要素、步骤或成分。如果在权利要求中，所述连接词将使所述权利要求限于所描述的材料而不包含未描述的材料，但仍包含与那些所描述的材料通常相关的杂质。
当以范围、优选范围或一系列上限优选值和下限优选值给出数量、浓度或其它数值或参数时，这理解为明确公开了由任何成对的任何范围上限或优选的值和任何范围下限或优选的值形成的全部的范围，而无论 所述范围是否分别被公开。例如当描述了“1至5”的范围时，所述范围应当解释为包括范围“1至4”、“1至3”、“1至2”、“1至2和4至5”、“1至3和5”等。在提及数字值范围之处，除非另有指示，否则该范围旨在包括其端点和处于该范围内的全部整数和分数。
当使用术语“约”来描述值或范围端点值时，所述公开的内容应当理解为包括所提及的具体值或端值。
本发明人出人意料地发现当在含硅负极的含羧基的粘结剂中引入由结构式I表示的聚合物时，可以显著改善包含该含硅负极的锂离子电池的循环稳定性和库仑效率。不受理论的约束，据信这种改善是归因于该粘结剂的不同组分之间的协同作用和与硅颗粒的强的化学键合。以DMA，MEA和PAA为例，p(DME-co-MEA)具有较好的弹性和粘性，例如，MEA包括大量C-O键，使得聚合物具有弹性，在经受巨大的体积膨胀后，形变可恢复；DMA中含有酚羟基与MEA形成氢键，使得聚合物具有粘性。此外，它有助于形成硅负极的稳定的SEI层。考虑到便利的溶液制备方法和生态友好以及低成本等因素，该新型的互穿凝胶粘结剂在下一代锂离子电池中用作高容量硅负极具有极大的潜力，并且也可以用作需要经受大的体积改变的其它电极材料。
在本发明中，含羧基的粘结剂包括聚丙烯酸、羧甲基纤维素、海藻酸和多糖，所述多糖包括氧化淀粉、卡拉胶和黄原胶等。在本发明的一个优选实施方式中，含羧基的粘结剂是聚丙烯酸。
在本发明的一个实施方式中，复合粘结剂包含PAA与聚(多巴胺甲基丙烯酰胺-共-丙烯酸甲氧基乙酯)(简称为p(DMA-co-MEA))的混合物，其中PAA与p(DMA-co-MEA)的重量比为0.1∶1至10∶1的范围，优选0.5∶1至7∶1的范围，更优选1∶1至4∶1的范围。
在本发明的另一实施方式中，聚(多巴胺甲基丙烯酰胺-共-丙烯酸甲氧基乙酯)(p(DMA-co-MEA))由丙烯酸甲氧基乙酯(MEA)与多巴胺甲基丙烯酰胺(DMA)的共聚获得，其中，多巴胺甲基丙烯酰胺与丙烯酸甲氧基乙酯的摩尔比为1∶1至1∶20的范围，优选1∶5至1∶18的范围，更优选1∶7.5至1∶15的范围。
在本发明中，设计并合成了由PAA和p(DMA-co-MEA)混合形成的新型的凝胶状粘结剂。在充放电过程中的体积改变可以有效地由这种弹性的粘结剂抑制。该粘结剂通过交联和形成共价键与氢键共存从而显示在Si上的高机械强度的键合以及特别的3D网络。与纯的PAA粘结剂相比，该改性的粘结剂可以有效地容纳在嵌锂/脱锂过程中Si负极的巨大的体积改变，同时保持更好的循环稳定性和更高的库仑效率，即使在高的电流密度和高的负载下。
使用该改性的粘结剂的电池的循环性能优于PAA粘结剂。对于硅-石墨复合负极，与使用PAA粘结剂的低于60％的容量保留率相比，使用该改性粘结剂的本发明实现了在200圈循环高达91％的容量保留率。并且，对于硅负极，使用该改性粘结剂的电池性能也优于使用PAA粘结剂的那些。此外，本发明也测试了在锂电池中硅-石墨复合负极和使用不同粘结剂的硅负极的C-倍率性能。已证实使用该改性粘结剂的电池的C-倍率性能优于使用PAA粘结剂的那些。
本发明的另一优点在于合成方法易于实现以及容易放大。
实施例
实施例1
制备根据本发明的复合粘结剂A1
合成DMA
将20g硼酸钠和8g的NaHCO3溶解于200ml的去离子水中，并用Ar鼓泡20分钟。然后加入10g的多巴胺HCl盐(52.8mmol)，随后逐滴加入9.4ml的甲基丙烯酸酐(58.1mmol)在50ml的THF中，在此期间，将溶液的pH值保持在8以上，并根据需要加入1M的NaOH。反应混合物在室温下伴随Ar鼓泡搅拌过夜。用100ml的乙酸乙酯冲洗含水混合物两遍，然后将含水溶液的pH降低至小于2并用100ml的乙酸乙酯萃取三次。将最终的三次乙酸乙酯层合并，在MgSO4上干燥以将体积降低至约50ml。在剧烈搅拌下加入450ml的己烷，将悬浮液保持在4℃过夜。从己烷中重结晶产物，并干燥以得到9.1g的灰色固体DMA。
合成p(DMA-co-MEA)
将12.5ml的MEA(丙烯酸甲氧基乙酯，商购自Acros，98％)通过填充有30g的Al2O3的柱以除去阻聚剂。将7.5g纯化的MEA(57.7mmol)、1.7g的上述制备得到的DMA(7.7mmol)和106g偶氮二异丁腈(0.64mmol)加入至长颈烧瓶中的20ml的DMF中。通过pump-freeze-thaw循环三次脱气溶液混合物。当在真空下密封时，将溶液加热至60℃并搅拌过夜。用5ml的甲醇稀释反应混合物，并加入至400ml的Et2O以沉淀聚合物。在DCM/Et2O中再沉淀两次并在真空干燥器中干燥后，获得5.7g白色的粘性的固体聚合物。将聚合物溶于甲醇中并使用具有分子量截留为12-14kDa的渗析膜相对于甲醇进行渗析。在渗析后，挥发甲醇以得到白色固体的纯产物(产率约90％)，GPC(Mn＝252kDa)。将该聚合物称为P1。
制备根据本发明的复合粘结剂A1
将上述制得的聚合物P1在NMP溶液中与PAA(Sigma Aldrich)以P1与PAA的重量比为1∶4进行混合以形成本发明实施例1的复合粘结剂A1(也表示为PAA-c-P1)。
实施例2
制备根据本发明的复合粘结剂A2
除了通过如表1中所示的不同比例的DMA和MEA的聚合获得P2之外，以与实施例1相同的操作，制备根据本发明的复合粘结剂A2(也表示为PAA-c-P2)。
表1在合成P1、P2、P3和P4中DMA和MEA的不同摩尔比
摩尔比 DMA MEA
P1 1 7.5
P2 1 10
P3 1 13
P4 1 15
实施例3
制备根据本发明的复合粘结剂A3
除了通过如表1中所示的不同比例的DMA和MEA的聚合获得P3之外，以与实施例1相同的操作，制备根据本发明的复合粘结剂A3(也表示为PAA-c-P3)。
实施例4
制备根据本发明的复合粘结剂A4
除了通过如表1中所示的不同比例的DMA和MEA的聚合获得P4之外，以与实施例1相同的操作，制备根据本发明的复合粘结剂A4(也表示为PAA-c-P4)。
实施例5
制备根据本发明的复合粘结剂A5
将上述制得的聚合物P2在NMP溶液中与PAA(Sigma Aldrich)以P2与PAA的重量比为1∶2进行混合以形成本发明的复合粘结剂A5。
实施例6
制备根据本发明的复合粘结剂A6
将上述制得的聚合物P2在NMP溶液中与PAA(Sigma Aldrich)以P2与PAA的重量比为1∶1进行混合以形成本发明的复合粘结剂A6。
实施例7
制备根据本发明的复合粘结剂A7
合成p(DMA-co-HEA)
将8.9g HEA(77mmol，丙烯酸-2-羟乙酯，商购自Acros，98％)、1.7g的上述制备得到的DMA(7.7mmol)和106g偶氮二异丁腈(0.64mmol)加入至在气密烧瓶中的20ml的DMF中。通过pump-freeze-thaw循环三次脱气溶液混合物。当在真空下密封时，将溶液加热至60℃并搅 拌过夜。用5ml的甲醇稀释反应混合物，并加入至400ml的Et2O以沉淀聚合物。在DCM/Et2O中再沉淀两次并在真空干燥器中干燥后，获得5.7g白色的粘性的固体聚合物。将聚合物溶于甲醇中并使用具有分子量截留为12-14kDa的渗析膜相对于甲醇进行渗析。在渗析后，挥发甲醇以得到白色固体的纯产物(产率约90％)，GPC(Mn＝252kDa)。将该聚合物称为P5。
制备根据本发明的复合粘结剂A7
将上述制得的聚合物P5在NMP溶液中与PAA(Sigma Aldrich)以P5与PAA的重量比为1∶4进行混合以形成本发明实施例7的复合粘结剂A7。
对比例1
为了对比，使用在NMP中的聚(丙烯酸)(Alfa Aesar，平均重均分子量＝240 000)作为对比粘结剂C1(也表示为PAA)。
对比例2
为了对比，使用在NMP中的PAA与聚丙烯酸甲氧基乙酯的混合物，简称为PAA-c-p(MEA)作为对比粘结剂C2。
其中，如下合成p(MEA)：将5g纯化MEA单体溶于20mL DMF中，加入AIBN 60mg，转移至长颈烧瓶中，通过pump-freeze-thaw循环三次脱气溶液混合物。当在真空下密封时，将溶液加热至60℃并搅拌过夜。用5ml的甲醇稀释反应混合物，并加入至400ml的Et2O以沉淀聚合物。在DCM/Et2O中再沉淀两次并在真空干燥器中干燥后，获得4.0g无色透明的粘性的固体聚合物。将聚合物溶于甲醇中并使用具有分子量截留为12-14kDa的渗析膜相对于甲醇进行渗析。
对比例3
为了对比，使用在NMP中的PAA与聚多巴胺甲基丙烯酰胺的混合 物，简称为PAA-c-p(DMA)作为对比粘结剂C3。
其中，如下合成p(DMA)：DMA单体粉末2g溶于10mL DMF中，加入AIBN 30mg，转移至长颈烧瓶中，通过pump-freeze-thaw循环三次脱气溶液混合物。当在真空下密封时，将溶液加热至60℃并搅拌过夜。用5ml的甲醇稀释反应混合物，并加入至400ml的Et2O以沉淀聚合物。在DCM/Et2O中再沉淀两次并在真空干燥器中干燥后，获得1.2g灰色的粘性的固体聚合物。将聚合物溶于甲醇中并使用具有分子量截留为12-14kDa的渗析膜相对于甲醇进行渗析。
电极的制备
含Si与石墨作为负极活性材料的电极的制备
将活性材料Si粉末(Alfa Aesar)、石墨、炭黑导电剂Super P(40nm，Timical)和上述制备的复合粘结剂以重量比为35∶45∶7∶13混合，搅拌均匀后涂覆至Cu箔上，之后干燥电极，切至12mm直径的圆盘，在3MPa下压制，最后在70℃下热处理硅电极5小时，然后在真空下升温至150℃保持4小时。
仅含Si作为负极活性材料的电极的制备
将活性材料Si粉末(Alfa Aesar)、炭黑导电剂Super P(40nm，Timical)和上述制备的复合粘结剂以重量比分别为6∶2∶2或8∶1∶1混合，搅拌均匀后涂覆至Cu箔上，之后干燥电极，切至12mm直径的圆盘，在3MPa下压制，最后在70℃下热处理硅电极5小时，然后在真空下升温至150℃保持4小时。
电池组装和电化学测试
如上所述制备的复合粘结剂对于电化学性能的影响通过使用三个电极纽扣型电池来评价。
在充满氩气的手套箱(MB-10 compact，MBraun)中组装CR2016纽扣电池，使用在碳酸二甲酯(DMC)和碳酸亚乙酯(EC)的1∶1体积比 的混合溶剂中的1M的LiPF6，包括10重量％的碳酸氟亚乙酯(FEC)作为电解质，PE膜(Celgard 2400)作为隔膜和锂金属作为对电极。在LAND电池测试系统(CT 2007A，武汉蓝田公司)上在25℃进行恒流充放电测试，评价循环性能。对于放电(锂嵌入)，截止电压是0.01V(相对于Li+/Li)，对于充电(Li脱嵌)，截止电压是1.2V(相对于Li+/Li)。基于Si-石墨复合物或Si的重量计算比容量。在每个电极中的活性材料的重量负载为如下：当用硅-石墨作为负极活性材料时，其负载量为2mg/cm2，当仅用硅作为负极活性材料时，其负载量为0.8mg/cm2。
图2显示了当在锂离子电池中分别使用实施例1-4的复合粘结剂和对比例1-3的粘结剂时，含硅-石墨的负极的电化学性能。具体来说，图2(a)和(b)显示了在1C(分别在0.2C和0.5C两个循环后)下分别采用实施例1-4的复合粘结剂和对比例1-3的粘结剂的含硅-石墨的负极循环性能。
由图2(a)，可以看出，当采用实施例1-4的复合粘结剂用于含硅-石墨的负极时，均获得了优于使用PAA作为粘结剂的含硅-石墨的负极的循环性能，其中，以实施例2的复合粘结剂A2的效果最佳，依次为实施例3、实施例1和实施例4。
图2(b)显示了分别采用实施例2的复合粘结剂A2与各自采用PAA、PAA-c-p(MEA)和PAA-c-p(DMA)作为粘结剂的含硅-石墨的负极的循环性能比较，其中PAA-c-p(MEA)是指PAA与聚丙烯酸甲氧基乙酯的混合物，和PAA-c-p(DMA)是指PAA与聚多巴胺甲基丙烯酰胺的混合物。由图2(b)可以看出，采用PAA和采用PAA-c-p(MEA)的结果类似，二者均不利地在20圈循环后，容量下降近50％，而本发明实施例2的复合粘结剂A2获得了最优的结果。
图2(c)显示了分别采用PAA和本发明实施例2的A2(PAA-c-P2)作为粘结剂的含硅-石墨的负极的C-倍率性能。图2(d)显示了在1C(分别在0.2C和0.5C两个循环后)下200个循环时，分别采用PAA和本发明的实施例2的A2(PAA-c-P2)作为粘结剂的含硅-石墨的负极的循环性能。由上图可以看出，采用实施例2的A2作为复合粘结剂的含硅-石墨的负极 的倍率和循环性能相较于采用PAA作为粘结剂均有了明显提高。
由图2的结果可以看出，采用本发明的实施例1-4的复合粘结剂制备的电池均可获得优异的循环性能。
图3是显示不同重量比的PAA和P2聚合物(实施例2、5和6中的复合粘结剂)作为复合粘结剂在包含硅-石墨的负极的锂离子电池中的循环性能的图。从图中可以看出，当PAA和P2的重量比为4∶1时，电化学性能最佳。
为了进一步阐明本发明在循环性能方面所获得的出人意料的益处，图4显示了使用本发明的实施例2的A2(PAA-c-P2)作为粘结剂在1C(分别在0.2C和0.5C两个循环后)下循环1000圈的硅-石墨负极锂离子电池的延长的循环性能。由图4可以看出，当采用本发明的实施例2的复合粘结剂A2时，电池在200圈后可以保持91％的容量，并在500圈后保持80％的容量，甚至在1000圈后仍可以保持高于50％的容量。
本发明进一步考察了本发明的复合粘结剂在仅由硅组成的负极活性材料的电池中的性能。
除了将活性材料Si粉末、炭黑导电剂Super P(40nm，Timical)和制备的粘结剂的重量比分别设定为6∶2∶2、8∶1∶1之外，以与实施例1-4相同的方法制备电极并组装成电池。
图5显示了使用PAA和本发明实施例2的A2(PAA-c-P2)作为复合粘结剂的硅负极的锂离子电池的电化学性能。由该图可以看出，即使在仅由Si作为活性材料的负极中，当活性材料Si粉末、炭黑导电剂Super P(40nm，Timical)和粘结剂的重量比分别为6∶2∶2(图5(a)和图5(c))和8∶1∶1(图5(b)和图5(d))时，本发明实施例2的复合粘结剂所获得的循环和倍率性能的结果也明显优于由PAA作为粘结剂的结果。
图6显示了使用本发明实施例7的A7作为复合粘结剂的硅负极的锂离子电池的电化学性能。由该图可以看出，使用该复合粘结剂的含硅-石墨的负极的循环性能有了明显提高。
基于上述测试结果，可以看出，当将本发明的复合粘结剂用于负极复合材料制备锂离子电池时，显著地改善了电化学性能，尤其是通过改 善粘结剂与含Si活性材料之间的键合情况，显著改善了电池的循环和倍率性能。

Claims (10)

  1. 复合粘结剂，其包含：
    a)含羧基的粘结剂，和
    b)由结构式I表示的如下聚合物，
    Figure PCTCN2017082375-appb-100001
    其中，R为-CH3或-H，x∶y＝3∶1-16∶1，优选x∶y＝5∶1-12∶1，更优选x∶y＝6∶1-10∶1，z为0-6的整数，优选z为0-3之间的整数，更优选z为0-2之间的整数。
  2. 如权利要求1所述的复合粘结剂，其中，所述含羧基的粘结剂包括聚丙烯酸、羧甲基纤维素、海藻糖和多糖，其中，所述多糖包括氧化淀粉、卡拉胶和黄原胶。
  3. 如权利要求1或2所述的复合粘结剂，并且由结构式I表示的聚合物的数均分子量为200,000-500,000。
  4. 如权利要求1-3任一项所述的复合粘结剂，其中，所述含羧基的粘结剂与由结构式I表示的聚合物的重量比为0.1∶1至10∶1，优选0.5∶1至7∶1，更优选1∶1至4∶1。
  5. 如权利要求1-4任一项所述的复合粘结剂，其中，所述由结构式I表示的聚合物为聚(多巴胺甲基丙烯酰胺-共-丙烯酸甲氧基乙酯)，R为 -CH3，z＝0。
  6. 如权利要求1-3任一项所述的复合粘结剂，其中，所述由结构式I表示的聚合物为聚(多巴胺甲基丙烯酰胺-共-丙烯酸-2-羟乙酯)，R为-OH，z＝0。
  7. 电极材料，其包含如权利要求1至6任一项所述的复合粘结剂。
  8. 如权利要求7所述的电极材料，其中所述复合粘结剂的含量基于电极材料的重量为2-30重量％，优选5-25重量％，更优选10-20重量％。
  9. 锂离子电池，其包含如权利要求1至6任一项所述的复合粘结剂。
  10. 如权利要求1-6任一项所述的复合粘结剂的制备方法，其包括步骤：
    (1)将多巴胺甲基丙烯酰胺单体与由结构式II表示的单体进行自由基共聚；
    Figure PCTCN2017082375-appb-100002
    其中，R为-CH3或-H，z为0-6的整数，优选z为0-3之间的整数，更优选z为0-2之间的整数，并且，多巴胺甲基丙烯酰胺单体与由结构式II表示的单体的摩尔比在1∶1至1∶20，优选1∶5至1∶18，更优选1∶7.5至1∶15的范围；和
    (2)将含羧基的粘结剂与步骤(1)中获得的共聚物进行物理混合。
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