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WO2018000578A1 - 多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用 - Google Patents

多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用 Download PDF

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WO2018000578A1
WO2018000578A1 PCT/CN2016/098378 CN2016098378W WO2018000578A1 WO 2018000578 A1 WO2018000578 A1 WO 2018000578A1 CN 2016098378 W CN2016098378 W CN 2016098378W WO 2018000578 A1 WO2018000578 A1 WO 2018000578A1
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Prior art keywords
lithium ion
ion battery
polyvinyl alcohol
modified polyvinyl
binder
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English (en)
French (fr)
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张灵志
汪靖伦
何嘉荣
苏静
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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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
    • 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
    • H01M4/623—Binders being polymers fluorinated 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a polymer lithium ion battery binder, in particular to a multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder and application in an electrochemical energy storage device.
  • the binder is an important inactive component of the lithium ion battery in which the electrode active material and the conductive agent are adhered to the current collector, and the performance of the battery directly affects the electrochemical performance of the battery.
  • the binder In addition to requiring a good bonding between the electrode active material, the conductive agent and the current collector, the binder should have a sufficiently good dispersibility, thereby facilitating the conduction of electrons and ions during charging and discharging, and reducing The impedance between the current collector and the electrode material; in addition, the adhesive should have sufficient elasticity to prevent the active material particles from loosening and falling off due to their expansion and contraction during charging and discharging of the battery.
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • the search for a new type of green binder that can replace PVDF has far-reaching significance and has gradually become an important development direction of lithium ion battery binder.
  • Acetal modified PVA resin (CN105518914A) and PVA graft copolymerized polymer (CN105637686A) can be used as an oil binder for lithium ion batteries; Modified PVA composite polyacrylic acid can be used as an aqueous binder in silicon negative electrode lithium ion batteries (Journal of Power Sources 298 (2015) 8-13); PVA as emulsifier, styrene monomer and acrylate monomer Copolymerization (CN105261759A) can be used to prepare aqueous binders for lithium ion batteries, but polystyrene is disadvantageous in that it is brittle, low in impact strength, prone to stress cracking, and poor heat resistance. Research and development of new PVA-based lithium-ion battery water-based binder to improve its bonding performance, further improve battery performance and reduce production costs, especially for the development of corresponding aqueous binder for the positive electrode is the current hot spot.
  • the object of the present invention is to provide a multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder, which has good water-soluble acrylic acid and its salts, good bonding properties and electrochemical properties of acrylonitrile, Or a well-flexible acrylamide monomer is bonded to the PVA molecule by a Michael addition reaction, and the prepared aqueous binder has good water solubility, and can improve the uniformity of the electrode slurry during the preparation of the lithium ion battery electrode sheet.
  • the electrode slurry can form a film uniformly and flatly on the current collector; it can enhance the bonding strength between the electrode active material, the conductive agent and the current collector, and is favorable for the electron/ion in the charging and discharging process.
  • Conduction reduces the electrochemical interface impedance of the pole piece, greatly improves the high rate performance of the positive and negative materials of the lithium battery, and the cycle stability performance, does not drop the material, and does not cause a decrease in capacity, thereby effectively extending the battery life.
  • the Michael addition reaction can controllably introduce functional monomers into the PVA molecule, so that the prepared binder product has stable and uniform quality and good comprehensive performance.
  • a multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder which uses polyvinyl alcohol as a substrate, hydrophilic monomer and oleophilic monomer as functional modified monomers, via Michael
  • the Michael addition reaction means that one or more of polyvinyl alcohol and one of a hydrophilic monomer and a lipophilic monomer are reacted by a basic catalyst at a temperature of from 0 to 90 °C.
  • the basic catalyst is preferably one or more of LiOH, NaOH, LiOH/urea, NaOH/urea; and the catalyst is used in an amount of 0.1 to 10% by weight based on the total mass of the monomers.
  • the invention also provides a preparation method of the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder, comprising the following steps:
  • the step 2) adding a basic catalyst to the solution obtained in the step 1), stirring well to obtain a mixed solution; adding a hydrophilic monomer and a lipophilic monomer at 0 to 90 ° C and stirring the reaction for 1 to 9 hours to obtain a multi-functionalized modified a polyvinyl alcohol-based lithium ion battery aqueous binder; adjusting the solubility of the binder by adjusting the mass ratio of the hydrophilic monomer and the lipophilic monomer; The amount is 0.1 to 10% of the total mass of the monomer; the molecular weight of the polyvinyl alcohol is 10,000 to 250,000, and the molar ratio of the hydroxyl group-containing repeating polymerization unit, the hydrophilic monomer, and the lipophilic monomer of the polyvinyl alcohol is 1:0.01. ⁇ 1:0 to 0.99; the basic catalyst is used in an amount of 0.1 to 10% by weight based on the total mass of the monomers.
  • the protective gas of step 1) is nitrogen and/or argon;
  • step 2 the stirring reaction temperature is 80 °C. ;
  • the stirring reaction time of the step 2) is 8 hours; the basic catalyst is selected from one or more of LiOH, NaOH, LiOH/urea, NaOH/urea.
  • the invention also protects that the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder can be directly applied to the positive or negative electrode sheets of the lithium ion battery, and the binder can also be prepared with LiOH, Li 2 CO. 3 , NaOH and other alkalis are neutralized and then applied to the positive or negative electrode of lithium ion batteries.
  • the positive electrode sheet of the lithium ion battery comprises a current collector and a positive electrode of a lithium ion battery supported on the current collector a slurry;
  • the lithium ion battery positive electrode slurry includes a positive electrode active material, a conductive agent, the multi-functionalized modified polyvinyl alcohol-based lithium ion battery binder, and a solvent;
  • the positive electrode active material is selected from lithium iron phosphate, lithium cobaltate, lithium manganate Or one or more of a ternary material (LiNi 1/3 Mn 1/3 Co 1/3 O 2 , NMC);
  • the conductive agent is acetylene black;
  • the current collector is
  • the multi-functionalized modified polyvinyl alcohol-based lithium ion battery binder is used in a lithium ion battery negative electrode sheet, and the lithium ion battery negative electrode sheet comprises a current collector and a lithium ion battery negative electrode slurry supported on the current collector
  • the lithium ion battery negative electrode slurry includes a negative electrode active material, a conductive agent, the multi-functionalized modified polyvinyl alcohol-based lithium ion battery binder, and a solvent; the negative electrode active material, the conductive agent, and the plurality of materials
  • the mass ratio of the functionalized modified polyvinyl alcohol-based lithium ion battery binder is 70 to 95:1 to 20:4 to 10; the negative electrode active material is selected from one of silicon-based materials, lithium titanate or graphite. Two or more; the conductive agent is acetylene black; and the current collector is copper foil.
  • the binder is applied to other electrochemical energy storage devices such as other secondary batteries, supercapacitors, or solar cells.
  • the invention also provides a lithium ion battery comprising a battery case, a pole core and an electrolyte, the pole core and the electrolyte being sealed in the battery case, the pole core comprising the plurality of An electrode of a functionalized modified polyvinyl alcohol based lithium ion battery binder and a separator positioned between the electrodes.
  • the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder provided by the present invention is compared with the graft polymer functional modified PVA binder (CN105637686A, CN105261759A), and the invention is subjected to Michael addition reaction.
  • the functional monomer can be controlled to be introduced into the PVA molecule, so that the prepared binder product has stable and uniform quality and good comprehensive performance.
  • the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder provided by the invention has good water solubility, elasticity and bonding property, and can be used for improving electrode paste in the preparation process of lithium ion battery electrode sheets. Uniformity, so that the electrode slurry can form a film uniformly and flatly on the current collector; therefore, the pole piece does not fall off, does not cause a decrease in capacity, and greatly improves the high magnification of the positive and negative materials of the lithium ion battery. Performance and cycle stability to extend battery life.
  • the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder provided by the invention is applied to the positive and negative electrodes of the lithium ion battery, and can enhance the bonding strength between the electrode active material, the conductive agent and the current collector, Conducive to the conduction of electrons/ions during charge and discharge, reduce the electrochemical interface impedance of the pole piece, and greatly improve the high rate performance and cycle stability of the positive and negative materials of the lithium battery.
  • the preparation method of the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder provided by the invention is simple, green, environmentally friendly, rich in resources, can significantly reduce the cost, and has broad market prospect; the lithium ion battery can be applied.
  • Positive and negative electrodes can promote the technological progress of the lithium-ion battery industry, and even promote the development of strategic emerging industries such as electric vehicles.
  • the binder is applied to other electrochemical energy storage devices such as other secondary batteries, supercapacitors, or solar cells.
  • Fig. 1 is an infrared contrast spectrum of an aqueous binder of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery obtained in Example 1-3 of the present invention.
  • Example 2 is a graph showing the peel strength of an aluminum alloy foil of an aqueous binder of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery obtained in Example 1-3 of the present invention.
  • Example 3 is a graph showing the peel strength of different aqueous materials of the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder obtained in Example 3 of the present invention.
  • Example 4 is a comparison of voltage-specific capacity of the first discharge of the multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder and the lithium iron phosphate LiFePO 4 /Li battery with PVDF binder obtained in Example 3 of the present invention; Graph.
  • Example 5 is a cyclic voltammetric comparison diagram of an aqueous binder of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery obtained in Example 3 of the present invention and a lithium iron phosphate LiFePO 4 /Li battery using a PVDF binder.
  • Example 6 is a cycle performance of a lithium iron phosphate LiFePO 4 /Li battery of an aqueous binder of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery obtained in Example 3 of the present invention.
  • Example 7 is a circuit impedance of a ternary LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li battery of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder obtained in Example 3 of the present invention; Figure.
  • Example 8 is a graph showing the rate performance of a ternary LiNi 1/3 Co 1/3 Mn 1/3 O 2 /Li battery of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder obtained in Example 3 of the present invention. .
  • Fig. 9 is a graph showing the cycle performance of a silicon-based Si/Li battery of an aqueous binder of a multi-functionalized modified polyvinyl alcohol-based lithium ion battery obtained in Example 3 of the present invention.
  • Figure 10 is a comparison diagram of the flatness of the coating films of different electrode materials (positive electrode: LFP, NMC; negative electrode: Si, Graphite) according to Examples 1-3 of the present invention.
  • the binder preparation method in this embodiment is referred to in Example 1, except that the monomer to be added is a mixture: 2.5 g of acrylic acid and 0.84 g of acrylonitrile, a hydroxyl group-containing repeating polymerization unit of polyvinyl alcohol, an acrylic monomer, and The molar ratio of acrylonitrile monomer is 1:0.51:0.23, the reaction temperature is 80 ° C, and the white glue is obtained, and then neutralized to pH 6-7 with LiOH, which is a multifunctional functionalized modified polyvinyl alcohol-based lithium ion.
  • Battery water-based binder
  • the binder preparation method in this embodiment is referred to in Example 1, except that the monomer to be added is a mixture: 2.5 g of acrylic acid, 0.84 g of acrylonitrile, and 1 g of acrylamide, a hydroxyl group-containing repeating polymerization unit of polyvinyl alcohol, acrylic acid.
  • the molar ratio of the monomer, the acrylonitrile monomer, and the acrylamide monomer is 1:0.51:0.23:0.21, the reaction temperature is 80 ° C, and the white gum is obtained, and then neutralized to pH 6-7 with LiOH.
  • Multifunctionalized modified polyvinyl alcohol based lithium ion battery aqueous binder Multifunctionalized modified polyvinyl alcohol based lithium ion battery aqueous binder
  • Fig. 1 is an infrared contrast spectrum of an aqueous binder of a multi-functionalized modified polyvinyl alcohol lithium ion battery obtained in Example 1-3 of the present invention.
  • Example 2 and Example 3 in addition to the stretching vibration signal of the carbonyl group, there is 2250 cm - 1 wave number - CN vibration signal.
  • AA AA
  • AN acrylonitrile
  • AM acrylamide
  • Table 1 is a table showing the viscosity of the aqueous binder of the multi-functionalized modified polyvinyl alcohol-based lithium ion battery obtained in Example 1-3, the peeling force against the current collector aluminum foil, and the average peel strength.
  • the average peel strength in the table is measured by first preparing a pure binder electrode sheet: directly coating 2 wt% of the binder on the Al foil, coating a thickness of 200 ⁇ m, and then testing the peel strength. Test method: intercepting a section The electrode sheets having a width of 15 mm were then tested by a peeling tester (Shenzhen, Kay Strong 180° peeling tester) (peeling speed was 20 mm/min), and finally summarized into a table.
  • the white glue liquid synthesized in Example 3 was used as an aqueous binder.
  • the positive electrode tab of the lithium ion battery includes a current collector and a lithium ion battery positive electrode slurry supported on the current collector;
  • the lithium ion battery positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and a solvent;
  • the binder is a white glue liquid synthesized in Example 3; and the mass ratio of the positive electrode active material, the conductive agent, and the binder is a positive electrode active material :
  • Conductive agent: binder 90:5:5, the solvent is water.
  • the positive active material is lithium iron phosphate (LiFePO 4 , LFP); the conductive agent is acetylene black; the current collector is aluminum foil current collector; the lithium ion battery positive electrode slurry has a solid content of 45%, lithium ion The viscosity of the battery positive electrode slurry was 3000 mPa ⁇ s.
  • the LFP and the conductive agent are mixed and stirred until uniformly dispersed; the glue liquid synthesized in Example 3 is added into the above system as an aqueous binder, stirred uniformly, and an appropriate amount of deionized water is added to adjust the viscosity to obtain an LFP electrode slurry; The obtained slurry was uniformly coated on an Al foil and dried under vacuum at 90 ° C to obtain an LFP positive electrode sheet.
  • a comparative battery was prepared in the same manner using PVDF as a binder and NMP as a solvent.
  • Electrochemical testing was performed on the charge and discharge performance of the test battery and the comparative battery.
  • FIG. 4 and FIG. 5 are respectively a voltage-specific capacity curve of the test battery and the comparative battery at a charge and discharge current density of 0.2 C and a cyclic voltammetry curve at a scan rate of 0.2 mV/s.
  • the LFP battery prepared by the multi-functionalized modified polyvinyl alcohol-based aqueous binder has a larger discharge capacity and a higher discharge platform, and the voltage interval between the redox peaks is relatively higher. Small, which means that it undergoes a smaller polarization process during discharge, demonstrating an improvement in the conductivity of the electrode system by the multi-functionalized modified polyvinyl alcohol-based aqueous binder.
  • the discharge specific capacity of the battery can reach 158 mAh/g, and the capacity retention rate is as high as 99%.
  • the ternary material was used as the positive electrode material, and the white glue liquid synthesized in Example 3 was used as the aqueous binder.
  • the positive electrode tab of the lithium ion battery includes a current collector and a lithium ion battery positive electrode slurry supported on the current collector;
  • the lithium ion battery positive electrode slurry includes a positive electrode active material, a conductive agent, a binder, and a solvent;
  • the binder is a white glue liquid synthesized in Example 3; and the mass ratio of the positive electrode active material, the conductive agent, and the binder is a positive electrode active material :
  • Conductive agent: binder 85:9:6, the solvent is water.
  • the positive active material is a ternary material (LiNi 1/3 Mn 1/3 Co 1/3 O 2 , NMC); the conductive agent is acetylene black; the current collector is an aluminum foil current collector; and the lithium ion battery
  • the solid content of the positive electrode slurry was 45 wt%, and the viscosity of the positive electrode slurry of the lithium ion battery was 3000 mPa ⁇ s.
  • Fig. 7 is an impedance diagram of the test battery before the cycle of the embodiment.
  • Fig. 8 is a graph showing the rate performance of the test battery of the present embodiment. It can be seen from the figure that the battery of the present embodiment has a small impedance characteristic, and the NMC battery prepared by using the multi-functionalized modified polyvinyl alcohol-based aqueous binder has good rate performance, and the battery is under the condition of 2C rate. The discharge specific capacity can still be as high as 112 mAh/g.
  • the white emulsion synthesized in Example 3 was used as an aqueous binder using a Si-based material as a negative electrode material.
  • the lithium ion battery negative electrode sheet comprises a current collector and a lithium ion battery negative electrode slurry supported on the current collector;
  • the lithium ion battery negative electrode slurry comprises a negative electrode active material, a conductive agent, a white emulsion synthesized in Example 3 as a binder and a solvent; and a mass ratio of the negative electrode active material, the conductive agent and the binder of 70:20:10, the solvent is water .
  • the negative active material is a Si-based material; the conductive agent is acetylene black; the current collector is a copper foil current collector; the lithium ion battery negative electrode slurry has a solid content of 45 wt%, and the lithium ion battery negative electrode slurry The viscosity was 3000 mPa ⁇ s.
  • the Si and the conductive agent are mixed and stirred until uniformly dispersed; the white emulsion synthesized in Example 3 is added to the above system as an aqueous binder, stirred uniformly, and an appropriate amount of deionized water is added to adjust the viscosity to obtain a Si electrode slurry; The obtained slurry was uniformly coated on a Cu foil and dried under vacuum at 60 ° C to obtain a Si-based negative electrode sheet.
  • FIG. 9 is a cycle performance test curve of a test battery at a charge and discharge current density of 400 mA/g in the present embodiment, and it can be seen from the figure that a multi-functionalized modified polyvinyl alcohol-based lithium ion battery aqueous binder is used as a bond.
  • the Si-based battery prepared by the agent has a first charge and discharge coulombic efficiency of 82%, and also initially exhibits good charge and discharge cycle performance.
  • Example 3 Using graphite as a negative electrode material, the white emulsion synthesized in Example 3 was used as an aqueous binder.
  • the graphite electrode was prepared in a manner in which the mass ratio of the negative electrode active material (graphite), the conductive agent, and the binder was 90:5:5.
  • Electrode sheet Binder Average peel strength (mN/mm)
  • Example 4 Lithium iron phosphate PVA-AA-AN-AM 61
  • Example 5 Ternary material PVA-AA-AN-AM 35
  • Example 6 Nano silicon powder PVA-AA-AN-AM 40
  • Example 7 graphite PVA-AA-AN-AM 60
  • Table 2 shows the peel strength of the electrode sheets of Example 4-7, and the thickness parameters at the time of coating: 100 ⁇ m of the positive electrode-LiFePO 4 , 100 ⁇ m of the ternary LiNi 1/3 Co 1/3 Mn 1/3 O 2 , and the negative electrode - Si was 80 ⁇ m and graphite was 50 ⁇ m. It can be seen from the experimental results that the multi-functionalized modified polyvinyl alcohol-based aqueous binder has a high peel strength, and the peel strength is enhanced compared to the polystyrene-containing binder system (CN 105261759A). One order of magnitude.
  • PVA-AA, PVA-AA-AN or PVA-AA-AN synthesized by using the graphite, the Si-based as the negative electrode material, the lithium iron phosphate and the ternary material as the positive electrode materials, respectively, using the examples 1, 2 or 3.
  • the -AM polymer lithium ion battery binder is used as a binder to form electrode sheets, and the flatness of the pole pieces is compared.
  • the preparation of the graphite electrode is referred to Example 7, except that the binder used is PVA-AA;
  • the preparation of the Si-based electrode is as in Reference Example 6, except that the binder used is PVA-AA-AN;
  • Example 4 The formulation of the LFP based electrode is referred to Example 4.
  • Example 5 The formulation of the NCM electrode is referred to Example 5.
  • test electrode sheets The flatness of the test electrode sheets was observed and compared.
  • Fig. 10 is a comparison diagram of the flatness of the pole pieces of the different test electrode sheets of the present embodiment. It can be seen from the figure that graphite, Si negative electrode sheets prepared by multi-functionalized modified PVA-AA, PVA-AA-AN polymer lithium ion battery binder, and multi-functionalized modified PVA-AA-
  • the lithium iron phosphate and ternary material positive electrode sheets prepared by AN-AM polymer lithium ion battery binder have excellent uniformity and flatness, no graininess or discontinuity, which is beneficial to improve the long cycle of the battery. Electrochemical stability, thereby improving the service life of the battery, has broad application prospects and development potential.

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Abstract

一种多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，该粘结剂以聚乙烯醇为底物，以亲水单体和亲油单体作为功能化改性单体，经迈克尔加成反应改性制备，具有良好的水溶性、弹性和粘结性能，应用于锂离子电池电极片制备过程中能提高电极浆料的均一性，从而使得电极浆料能在集流体上均匀性和平整性地成膜；因此，极片不掉料，不会造成容量下降，较大改善锂离子电池正负极材料的高倍率性能以及循环稳定性能、从而有效延长电池使用寿命。

Description

多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用 技术领域：
本发明涉及高分子锂离子电池粘结剂，具体涉及一种多元功能化改性聚乙烯醇基锂离子电池水性粘结剂及在电化学储能器件中的应用。
背景技术：
粘结剂是将电极活性物质和导电剂粘附在集流体上的锂离子电池重要非活性成分，其性能的优劣直接影响电池的电化学性能。除了要求其在电极活性物质、导电剂和集流体之间有着良好的粘结作用外，粘结剂应具有足够好的分散性，从而有利于电子、离子在充放电过程中的传导，减小集流体与电极材料之间的阻抗；另外，粘结剂应具有足够的弹性，从而可避免活性物质颗粒因自身在电池充、放电过程中的膨胀与收缩而松胀脱落。
目前在锂离子电池工业的规模化生产中主要采用溶于N-甲基吡咯烷酮(NMP)的聚偏氟乙烯(PVDF)作为粘结剂。但由于PVDF存在自身的缺点，如电子和离子导电性差，在电解液中有一定的溶胀，且与金属锂、LixC6在较高温度下发生放热反应，存在较大的安全隐患。此外，PVDF的杨氏模量相对较高，极片的柔韧性不够好，吸水后分子量下降，粘性变差，因此，其对环境的湿度要求比较高，能耗大，PVDF价格昂贵、生产成本高。因此，寻找可以替代PVDF的新型绿色粘结剂具有深远的意义，已逐渐成为锂离子电池粘结剂的重要发展方向。
开发水性粘结剂是锂离子电池粘结剂发展的一个重要方向。丁苯橡胶(SBR)/羧甲基纤维素钠(CMC)、聚丙烯酸酯类水性粘结剂已经有大规模市场应用，但其粘结力和抑制极片膨胀的效果均有限，故其使用范围受到一定的限制。聚乙烯醇(PVA)是合成水溶性树脂中的一种大宗产品，与天然产品淀粉、糊精及蛋白质类相比，合成的水溶性聚合物竞争优势在于产品质量稳定均一，综合性能较好。改性PVA用作锂离子电池粘结剂也有研究报道，缩醛改性PVA树脂(CN105518914A)和PVA接枝共聚高分子(CN105637686A)可用作油性粘结剂应用于锂离子电池；氰乙基化改性PVA复合聚丙烯酸可用作水性粘结剂应用于硅负极锂离子电池(Journal of Power Sources 298(2015)8-13)；PVA作为乳化剂、苯乙烯单体与丙烯酸酯类单体共聚(CN105261759A)可制备水性粘结剂应用于锂离子电池，但聚苯乙烯的不足之处在于性脆、冲击强度低、易出现应力开裂、耐热性差等。研究开发新型的PVA基锂离子电池水性粘结剂来提高其粘结性能，进一步改善电池性能，降低生产成本，尤其是针对正极开发相应的水性粘结剂更是当前的热点。
发明内容：
本发明的目的是提供一种多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，将具有良好水溶性的丙烯酸及其盐类、良好粘结性能和电化学性能的丙烯腈类、或良好柔顺性的丙烯酰胺单体通过迈克尔加成反应键连至PVA分子中，制备的水性粘结剂具有良好的水溶性，应用于锂离子电池电极片制备过程中能提高电极浆料的均一性，从而使得电极浆料能在集流体上均匀性和平整性地成膜；能增强电极活性物质、导电剂和集流体之间的粘结强度，有利于电子/离子在充放电过程中的传导，降低极片的电化学界面阻抗，较大改善锂电池正负极材料的高倍率性能以及循环稳定性能、不掉料，不会造成容量下降，从而可以有效延长电池使用寿命。相比较于聚合物功能改性PVA粘结剂，迈克尔加成反应能可控地将功能单体引入PVA分子中，从而使制备的粘结剂产品质量稳定均一，综合性能较好。
本发明是通过以下技术方案予以实现的：
一种多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，该粘结剂以聚乙烯醇为底物，以亲水单体和亲油单体作为功能化改性单体，经迈克尔加成反应改性制备的水溶性胶液，其固含量为2-50％，粘度为10～20000mPa·s；所述亲水单体为具有如下结构单体中的至少一种：CH2＝CR1R2；其中，R1选自-H、-CH3、-CH2CH3；R2选自-COOH、-COOLi、-COONa、-CONH2；所述亲油单体为具有如下结构的单体中的至少一种：CH2＝CR3R4；其中，R3选自-H、-CH3、-CH2CH3，R4选自-CN、-OCOCH3、-CONHCH3、-CON(CH3)2、和-COOR5中的至少一种，R5选自C1～C8烷基中的至少一种；所述聚乙烯醇的分子量为10000-250000，聚乙烯醇的含羟基重复聚合单元、亲水单体和亲油单体的摩尔比为1：0.01～1：0～0.99。
所述迈克尔加成反应指聚乙烯醇与亲水性单体和亲油性单体的一种或多种通过碱性催化剂引发在0～90℃的条件下反应。
所述碱性催化剂优选为LiOH、NaOH、LiOH/尿素、NaOH/尿素中的一种或两种以上；所述催化剂的用量为单体总质量的0.1～10wt％。
本发明还提供所述多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的制备方法，包括以下步骤：
1)首先将聚乙烯醇溶解于去离子水中，并在保护性气气氛下充分搅拌0.5～2.5小时驱除氧得到均一、分散性好的溶液；
2)将碱性催化剂加到步骤1)得到的溶液中，充分搅拌得到混合溶液；再加入亲水单体和亲油单体0～90℃搅拌反应1～9小时制得多元功能化改性的聚乙烯醇基锂离子电池水性粘结剂；通过调节亲水单体和亲油单体的质量比来调控粘结剂的溶解性；所述碱性催化剂的 用量为单体总质量的0.1～10％；所述聚乙烯醇分子量为10000-250000，并且聚乙烯醇的含羟基重复聚合单元、亲水性单体和亲油性单体的摩尔比为1：0.01～1：0～0.99；所述碱性催化剂的用量为单体总质量的0.1～10wt％。
优选地，步骤1)所述保护性气为氮气和/或氩气；
优选地，步骤2)；所述搅拌反应温度为80℃。；
优选地，步骤2)所述搅拌反应时间为8h；所述碱性催化剂选自LiOH、NaOH、LiOH/尿素、NaOH/尿素中的一种或两种以上。
本发明还保护所述多元功能化改性聚乙烯醇基锂离子电池水性粘结剂可直接应用于锂离子电池正或负极片中的，也可以制得的粘结剂用LiOH，Li2CO3,NaOH等碱中和后再应用于锂离子电池正或负极片中的。
所述多元功能化改性聚乙烯醇基锂离子电池水性粘结剂在锂离子电池正极片中的应用，所述锂离子电池正极电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂、所述多元功能化改性聚乙烯醇基锂离子电池粘结剂和溶剂；所述正极活性材料、导电剂和所述多元功能化改性聚乙烯醇基锂离子电池粘结剂的质量比为＝70～95:1～20:4～10；所述正极活性材料选自磷酸铁锂、钴酸锂、锰酸锂或三元材料(LiNi1/3Mn1/3Co1/3O2，NMC)的一种或多种；所述导电剂为乙炔黑；所述集流体为铝箔；所述锂离子电池正极浆料的固体含量为30～75％，锂离子电池正极浆料的粘度为3000～8000mPa·s。
所述多元功能化改性聚乙烯醇基锂离子电池粘结剂在锂离子电池负极片中的应用，所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂、所述多元功能化改性聚乙烯醇基锂离子电池粘结剂和溶剂；所述负极活性材料、导电剂和所述多元功能化改性聚乙烯醇基锂离子电池粘结剂的质量比为70～95:1～20:4～10；所述负极活性材料选自硅基材料、钛酸锂或石墨的一种或两种以上；所述导电剂为乙炔黑；所述集流体为铜箔。
所述粘结剂应用于其它电化学储能器件，如其它二次电池、超级电容器、或太阳能电池。
本发明还提供了一种锂离子电池，所述锂离子电池包括电池壳、极芯和电解液，所述的极芯和电解液密封于电池壳内，所述的极芯包括含所述多元功能化改性聚乙烯醇基锂离子电池粘结剂的电极和位于电极之间的隔膜。
本发明具有如下有益效果：
1)本发明提供的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，相比较于接枝聚合物功能改性PVA粘结剂(CN105637686A,CN105261759A)，本发明通过迈克尔加成反应能可控地将功能单体引入PVA分子中，从而使制备的粘结剂产品质量稳定均一，综合性能较好。
2)本发明提供的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，具有良好的水溶性、弹性和粘结性能，应用于锂离子电池电极片制备过程中能提高电极浆料的均一性，从而使得电极浆料能在集流体上均匀性和平整性地成膜；因此，极片不掉料，不会造成容量下降，较大改善锂离子电池正负极材料的高倍率性能以及循环稳定性能、从而有效延长电池使用寿命。
3)本发明提供的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂应用于锂离子电池正负极，能增强电极活性物质、导电剂和集流体之间的粘结强度，有利于电子/离子在充放电过程中的传导，降低极片的电化学界面阻抗，较大改善锂电池正负极材料的高倍率性能以及循环稳定性能。
4)本发明提供的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的制备方法简便，绿色环保，资源丰富，能显著降低成本，具有广阔的市场前景；可应用锂离子电池的正、负极，能推动锂离子电池产业的技术进步，乃至推动电动汽车等战略新兴产业的发展具有重要意义。
5)所述粘结剂应用于其它电化学储能器件，如其它二次电池、超级电容器、或太阳能电池。
附图说明：
图1是本发明实施例1-3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的红外对比谱图。
图2为本发明实施例1-3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂对铝箔的剥离强度对比图。
图3为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂对不同电极材料的剥离强度图。
图4为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂与用PVDF粘结剂的磷酸铁锂LiFePO4/Li电池的首次放电的电压-比容量对比曲线图。
图5为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂与用PVDF粘结剂的磷酸铁锂LiFePO4/Li电池的循环伏安对比图。
图6为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的磷酸铁锂LiFePO4/Li电池的循环性能。
图7为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的三元LiNi1/3Co1/3Mn1/3O2/Li电池循环前的阻抗图。
图8为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的三元LiNi1/3Co1/3Mn1/3O2/Li电池的倍率性能图。
图9为本发明实施例3得到的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的硅基Si/Li电池的循环性能图。
图10本发明实施例1-3对不同电极材料(正极：LFP，NMC；负极：Si，Graphite)的涂膜平整性对比图。
具体实施方式：
以下是对本发明的进一步说明，而不是对本发明的限制。
实施例1：
(1)首先将3克聚乙烯醇预先溶解于50ml去离子水(DI-Water)中，并在氩气气氛下充分搅拌0.5-2.5小时得到均一、分散性好的溶液；
(2)称取0.1g NaOH催化剂于(1)中的反应体系中，充分搅拌得到均一体系；加入2.5g丙烯酸单体，聚乙烯醇的含羟基重复聚合单元和丙烯酸单体的摩尔比为1：0.51，调节反应温度至80℃，一直保持搅拌状态，恒温反应8h，得到透明均一胶液，然后用LiOH中和至pH为6-7，为多元功能化改性聚乙烯醇基锂离子电池水性粘结剂；
实施例2：
本实施例中粘结剂制备方法参考实施例1，所不同的是：加入的单体为混合物：2.5g丙烯酸和0.84g丙烯腈，聚乙烯醇的含羟基重复聚合单元，丙烯酸单体，和丙烯腈单体的摩尔比为1：0.51：0.23，反应的温度为80℃，得到白色胶液，然后用LiOH中和至pH为6-7，为多元功能化改性聚乙烯醇基锂离子电池水性粘结剂；
实施例3：
本实施例中粘结剂制备方法参考实施例1，所不同的是：加入的单体为混合物：2.5g丙烯酸、0.84g丙烯腈和1g丙烯酰胺，聚乙烯醇的含羟基重复聚合单元，丙烯酸单体，丙烯腈单体，和丙烯酰胺单体的摩尔比为1：0.51：0.23：0.21，反应的温度为80℃，得到白色胶液，然后用LiOH中和至pH为6-7，为多元功能化改性聚乙烯醇基锂离子电池水性粘结剂；
图1是本发明实施例1-3得到的多元功能化改性聚乙烯醇锂离子电池水性粘结剂的红外 对比谱图。从图1中可以看出，实施例1在1668cm-1波数处有明显的羧基中C＝O的伸缩振动信号，而实施例2和实施例3除了有羰基的伸缩振动信号，还有2250cm-1波数处-CN的振动信号。
表1
Figure PCTCN2016098378-appb-000001
*丙烯酸简写为AA，丙烯腈简写为AN，丙烯酰胺简写为AM。
表1为实施例1-3制得的多元功能化改性聚乙烯醇基锂离子电池水性粘结剂的粘度、对集流体铝箔的剥离力及平均剥离强度表。表中平均剥离强度是这样测的，先制作纯粘结剂电极片：直接将2wt％粘结剂涂覆在Al箔上，涂覆厚度为200μm，然后测试其剥离强度，测试方法：截取一段宽度为15mm的电极片，然后采用剥离测试仪器(深圳，凯强力180°剥离测试仪)对其进行测试(剥离速度为20mm/min)，最后汇总成表。从多元功能化改性聚乙烯醇基锂离子电池水性粘结剂对集流体铝箔的平均剥离强度值可以看出，通过多元功能化改性，其剥离强度可达60-70mN/mm的数量级。其剥离强度如图2所示。
实施例4：
以磷酸铁锂为正极材料，利用实施例3中所合成的白色胶液为水性粘结剂。
一、测试电池的配制：
本发明所述锂离子电池正极电极片的一种实施例，所述锂离子电池正极电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂、粘结剂和溶剂；所述粘结剂为实施例3中所合成的白色胶液；且所述正极活性材料、导电剂和粘结剂的质量比为正极活性材料：导电剂：粘结剂＝90:5:5，所述溶剂为水。所述正极活性材料为磷酸铁锂(LiFePO4，LFP)；所述导电剂为乙炔黑；所述集流体为铝箔集流体；所述锂离子电池正极浆料的固体含量为45％，锂离子电池正极浆料的粘度为3000mPa·s。
将LFP和导电剂混合搅拌至均匀分散；再将实施例3中所合成的胶液为水性粘结剂加入上述体系中搅拌均匀，加适量去离子水调节粘度，得到LFP电极浆料；将制得的浆料均 匀涂覆于Al箔上，90℃真空干燥，即得LFP正极片。将真空干燥过的极片裁片称重后，将之在手套箱中组装在2025电池壳内，以锂片为对电极，以聚乙烯膜为隔膜，以1M LiPF6EC/DMC/DEC(v/v/v＝1/1)为电解液组装电池进行循环伏安测试、恒电流充放电测试。
二、对比电池的配制：
采用PVDF作为粘结剂，以NMP为溶剂，按同样的方法配制对比电池。
三、电化学测试：
对测试电池、对比电池的充放电性能进行电化学测试。
四、结果分析：
图4、图5分别为本实施例测试电池及对比电池在0.2C充放电电流密度下的电压-比容量曲线和在0.2mV/s扫描速率下的循环伏安曲线。从图中可以看出，采用多元功能化改性聚乙烯醇基水性粘结剂制备的LFP电池，其拥有更大的放电容量和更高的放电平台，且氧化还原峰之间的电压间隔相对较小，这意味着其在放电时经历更小的极化过程，证明了多元功能化改性聚乙烯醇基水性粘结剂对于电极体系传导性能的改善。
图6为本实施例测试电池在0.2C充放电电流密度下循环性能曲线，30循环后电池的放电比容量可达158mAh/g，其容量保持率高达99％。
实施例5：
以三元材料为正极材料，利用实施例3中所合成的白色胶液为水性粘结剂。
一、测试电极的配制：
本发明所述锂离子电池正极电极片的一种实施例，所述锂离子电池正极电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂、粘结剂和溶剂；所述粘结剂为实施例3中所合成的白色胶液；且所述正极活性材料、导电剂和粘结剂的质量比为正极活性材料：导电剂：粘结剂＝85:9:6，所述溶剂为水。所述正极活性材料为三元材料(LiNi1/3Mn1/3Co1/3O2，NMC)；所述导电剂为乙炔黑；所述集流体为铝箔集流体；所述锂离子电池正极浆料的固体含量为45wt％，锂离子电池正极浆料的粘度为3000mPa·s。
将NMC和导电剂混合搅拌至均匀分散；再将实施例3中所合成的胶液为水性粘结剂加入上述体系中搅拌均匀，加适量去离子水调节粘度，得到NMC电极浆料；将制得的浆料均匀涂覆于Al箔上，90℃真空干燥，即得NMC正极片。将真空干燥过的极片裁片称重后，将之在手套箱中组装在2025电池壳内，以锂片为对电极，以聚乙烯膜为隔膜，以1M LiPF6EC/DMC/DEC(v/v/v＝1/1)为电解液组装电池进行恒电流充放电测试。
二、电化学测试：
对测试电池进行阻抗测试、充放电性能测试。
三、结果分析：
图7为本实施例测试电池循环前的阻抗图。图8为本实施例测试电池的倍率性能图。从图中可以看出，本实施例电池具有较小的阻抗特性，采用多元功能化改性聚乙烯醇基水性粘结剂制备的NMC电池，具有良好的倍率性能，电池在2C倍率条件下的放电比容量仍然可高达112mAh/g。
实施例6：
以Si基为负极材料，利用实施例3中所合成的白色乳液为水性粘结剂。
一、测试电极的配制：
本发明所述锂离子电池负极电极片的一种实施例，所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂、实施例3中所合成的白色乳液作为粘结剂和溶剂；且所述负极活性材料、导电剂和粘结剂的质量比70:20:10，所述溶剂为水。所述负极活性材料为Si基材料；所述导电剂为乙炔黑；所述集流体为铜箔集流体；所述锂离子电池负极浆料的固体含量为45wt％，锂离子电池负极浆料的粘度为3000mPa·s。
将Si和导电剂混合搅拌至均匀分散；再将实施例3中所合成的白色乳液作为为水性粘结剂加入上述体系中搅拌均匀，加适量去离子水调节粘度，得到Si电极浆料；将制得的浆料均匀涂覆于Cu箔上，60℃真空干燥，即得Si基负极片。将真空干燥过的极片裁片称重后，将之在手套箱中组装在2025电池壳内，以锂片为对电极，以聚乙烯膜为隔膜，以1M LiPF6EC/DMC/DEC(v/v/v＝1/1)为电解液组装电池进行恒电流充放电测试。
二、电化学测试：
对测试电极、对比电极的充放电循环稳定性进行电化学测试。
三、结果分析：
图9为本实施例测试电池在400mA/g充放电电流密度下的循环性能测试曲线，从图中可以看出，采用多元功能化改性聚乙烯醇基锂离子电池水性粘结剂作为粘结剂制备的Si基电池的首次充放电库伦效率可达82％，也初步表现出了良好的充放电循环性能。
实施例7：
以石墨为负极材料，利用实施例3中所合成的白色乳液为水性粘结剂。
一、测试电极的配制：
参考实施例6，石墨电极的配制不同之处是，所述负极活性材料(石墨)、导电剂和粘结剂的质量比90:5:5。
表2
  电极片 粘结剂 平均剥离强度(mN/mm)
实施例4 磷酸铁锂 PVA-AA-AN-AM 61
实施例5 三元材料 PVA-AA-AN-AM 35
实施例6 纳米硅粉 PVA-AA-AN-AM 40
实施例7 石墨 PVA-AA-AN-AM 60
表2为其中实施例4-7电极片的剥离强度，涂膜时的厚度参数：正极-LiFePO4为100μm，三元LiNi1/3Co1/3Mn1/3O2为100μm，负极-Si为80μm，石墨-50μm。从实验结果可以看出，多元功能化改性的聚乙烯醇基水性粘结剂具有较高的剥离强度，相比较于含聚苯乙烯的粘结剂体系(CN 105261759A)，其剥离强度增强了一个数量级。
实施例8：
以石墨、Si基为负极材料，以磷酸铁锂、三元材料为正极材料，分别利用实施例1、2或实施例3所合成的PVA-AA、PVA-AA-AN或PVA-AA-AN-AM高分子锂离子电池粘结剂为粘结剂来制作电极片，并分别比较极片的平整性。
一、测试电极的配制：
石墨电极的配制参考实施例7，不同的之处是，所使用的粘结剂为PVA-AA；
Si基电极的配制参考实施例6，不同的之处是，所使用的粘结剂为PVA-AA-AN；
LFP基电极的配制参考实施例4。
NCM电极的配制参考实施例5。
二、极片平整性测试：
对测试电极片的平整性进行观察、对比。
四、结果分析：
图10为本实施例不同测试电极片的极片平整性对比图。从图中可以看出，采用多元功能化改性PVA-AA、PVA-AA-AN高分子锂离子电池粘结剂分别制备的石墨、Si负极片，以及采用多元功能化改性PVA-AA-AN-AM高分子锂离子电池粘结剂制备的磷酸铁锂、三元材料正极片，均拥有优良的均匀性和平整性，没有出现颗粒感或间断点，有利于提高电池长循环过程中的电化学稳定性，从而提高电池的使用寿命，拥有广阔的应用前景和发展潜力。

Claims (7)

  1. 一种多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，其特征在于，它是以聚乙烯醇为底物，以亲水单体和亲油单体作为功能化改性单体，经迈克尔加成反应改性制备的水溶性胶液，其固含量为2～50％，粘度为10～20000mPa·s；所述亲水单体为具有如下结构单体中的至少一种：CH2＝CR1R2；其中，R1选自-H、-CH3、-CH2CH3；R2选自-COOH、-COOLi、-COONa、-CONH2；所述亲油单体为具有如下结构的单体中的至少一种：CH2＝CR3R4；其中，R3选自-H、-CH3、-CH2CH3，R4选自-CN、-OCOCH3、-CONHCH3、-CON(CH3)2、和-COOR5中的至少一种，R5选自C1～C8烷基中的至少一种；所述聚乙烯醇的分子量为10000-250000，聚乙烯醇的含羟基重复聚合单元、亲水单体和亲油单体的摩尔比为1：0.01～1：0～0.99。
  2. 根据权利要求1所述多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，其特征在于，所述迈克尔加成反应指聚乙烯醇与亲水性单体和亲油性单体的一种或多种通过碱性催化剂引发在0～90℃的条件下反应；所述碱性催化剂的用量为单体总质量的0.1～10wt％。
  3. 根据权利要求2所述多元功能化改性聚乙烯醇基锂离子电池水性粘结剂，其特征在于，所述碱性催化剂选自LiOH、NaOH、LiOH/尿素、NaOH/尿素中的一种或两种以上。
  4. 权利要求1所述多元功能化改性聚乙烯醇基锂离子电池水性粘结剂在锂离子电池正极片中的应用，其特征在于，所述锂离子电池正极电极片包括集流体和负载在集流体上的锂离子电池正极浆料；所述锂离子电池正极浆料包括正极活性材料、导电剂、权利要求1所述多元功能化改性聚乙烯醇基锂离子电池粘结剂和溶剂；所述正极活性材料、导电剂和所述多元功能化改性聚乙烯醇基锂离子电池粘结剂的质量比为＝70～95:1～20:4～10；所述正极活性材料选自磷酸铁锂、钴酸锂、锰酸锂或三元材料的一种或多种；所述导电剂为乙炔黑；所述集流体为铝箔；所述锂离子电池正极浆料的固体含量为30～75％，锂离子电池正极浆料的粘度为3000～8000mPa·s。
  5. 权利要求1所述多元功能化改性聚乙烯醇基锂离子电池粘结剂在锂离子 电池负极片中的应用，其特征在于，所述锂离子电池负极电极片包括集流体和负载在集流体上的锂离子电池负极浆料；所述锂离子电池负极浆料包括负极活性材料、导电剂、权利要求1所述多元功能化改性聚乙烯醇基锂离子电池粘结剂和溶剂；所述负极活性材料、导电剂和所述多元功能化改性聚乙烯醇基锂离子电池粘结剂的质量比为70～95:1～20:4～10；所述负极活性材料选自硅基材料、钛酸锂或石墨的一种或两种以上；所述导电剂为乙炔黑；所述集流体为铜箔。
  6. 权利要求1所述多元功能化改性聚乙烯醇基锂离子电池粘结剂应用于电化学储能器件，其特征在于，所述电化学储能器件为超级电容器或太阳能电池。
  7. 一种锂离子电池，所述锂离子电池包括电池壳、极芯和电解液，所述的极芯和电解液密封于电池壳内，其特征在于，所述的极芯包括权利要求1或2所述多元功能化改性聚乙烯醇基锂离子电池粘结剂的电极和位于电极之间的隔膜。
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CN116053418A (zh) * 2023-01-31 2023-05-02 哈尔滨工业大学 一种锂电池干法电极、隔膜及电池-结构一体化材料的制备方法

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