[go: up one dir, main page]

WO2018000578A1 - Adhésif à l'eau à base d'alcool polyvinylique modifié multifonctionnel pour batterie au lithium-ion et son application dans un dispositif de stockage d'énergie électrochimique - Google Patents

Adhésif à l'eau à base d'alcool polyvinylique modifié multifonctionnel pour batterie au lithium-ion et son application dans un dispositif de stockage d'énergie électrochimique Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
lithium ion
ion battery
polyvinyl alcohol
modified polyvinyl
binder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2016/098378
Other languages
English (en)
Chinese (zh)
Inventor
张灵志
汪靖伦
何嘉荣
苏静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangzhou Institute of Energy Conversion of CAS
Original Assignee
Guangzhou Institute of Energy Conversion of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Guangzhou Institute of Energy Conversion of CAS filed Critical Guangzhou Institute of Energy Conversion of CAS
Publication of WO2018000578A1 publication Critical patent/WO2018000578A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621Binders
    • H01M4/622Binders being polymers
    • H01M4/623Binders being polymers fluorinated polymers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un adhésif à l'eau à base d'alcool polyvinylique (à base de PVA) modifié multifonctionnel pour des batteries au lithium-ion ; l'adhésif est préparé et modifié au moyen de la réaction d'addition de Michael, dans laquelle le PVA est utilisé en tant que substrat, et un monomère hydrophile ainsi qu'un monomère lipophile sont utilisés en tant que monomères de modification fonctionnels ; ledit adhésif présente de bonnes propriétés de solubilité dans l'eau, d'élasticité et de liaison, et peut être utilisé dans le procédé de préparation d'une feuille d'électrode de batterie au lithium-ion de manière à améliorer l'uniformité d'une pâte d'électrode, de sorte que la pâte d'électrode puisse former de manière uniforme et régulière un film sur un collecteur de courant. Par conséquent, la feuille d'électrode ne perd pas de matériaux, ce qui peut empêcher une chute de capacité, et améliorer considérablement la capacité de haut débit et la stabilité de cycle des matériaux positif et négatif de la batterie au lithium-ion, ce qui permet de prolonger efficacement la durée de vie de la batterie.
PCT/CN2016/098378 2016-06-28 2016-09-08 Adhésif à l'eau à base d'alcool polyvinylique modifié multifonctionnel pour batterie au lithium-ion et son application dans un dispositif de stockage d'énergie électrochimique Ceased WO2018000578A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610504108.3 2016-06-28
CN201610504108.3A CN105958075B (zh) 2016-06-28 2016-06-28 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

Publications (1)

Publication Number Publication Date
WO2018000578A1 true WO2018000578A1 (fr) 2018-01-04

Family

ID=56901861

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/098378 Ceased WO2018000578A1 (fr) 2016-06-28 2016-09-08 Adhésif à l'eau à base d'alcool polyvinylique modifié multifonctionnel pour batterie au lithium-ion et son application dans un dispositif de stockage d'énergie électrochimique

Country Status (2)

Country Link
CN (1) CN105958075B (fr)
WO (1) WO2018000578A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020090927A1 (fr) * 2018-10-31 2020-05-07 日本ゼオン株式会社 Composition de liant pour batterie secondaire et son procédé de fabrication, composition de bouillie pour batterie secondaire, couche fonctionnelle pour batterie secondaire et son procédé de fabrication, couche d'électrode pour batterie secondaire et batterie secondaire
CN111668489A (zh) * 2020-06-17 2020-09-15 上海洛法化工有限公司 一种混合型锂离子电池硅负极水系粘结剂及其制备工艺
CN115053376A (zh) * 2020-03-11 2022-09-13 宁德新能源科技有限公司 锂离子电池及电子装置
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
CN116315032A (zh) * 2021-12-20 2023-06-23 比亚迪股份有限公司 一种锂离子电池及其制备方法及动力车辆

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106866846B (zh) * 2017-03-09 2020-09-08 宣城研一新能源科技有限公司 一种锂离子电池用水性粘结剂及其制备方法和锂离子电池极片
CN108987751A (zh) * 2017-05-31 2018-12-11 宁德时代新能源科技股份有限公司 一种粘结剂及其二次电池
JP6424934B1 (ja) * 2017-09-28 2018-11-21 住友大阪セメント株式会社 リチウムイオン二次電池用正極材料、リチウムイオン二次電池用正極、リチウムイオン二次電池
CN109994703A (zh) * 2018-12-29 2019-07-09 广东工业大学 电池电极粘结剂、电极及锂离子电池
KR101993728B1 (ko) * 2019-02-01 2019-06-28 (주)노루페인트 이차전지의 전극용 바인더 수지, 이차전지용 음극 및 이를 포함하는 리튬 이차전지
CN111354948B (zh) * 2020-03-27 2021-04-27 成都翊昂科技有限公司 锂离子电池三元高镍正极粘合剂及其制备方法
CN112467133B (zh) * 2020-03-30 2022-03-18 万向一二三股份公司 一种锂离子电池负极浆料及其制备方法
CN111668490B (zh) * 2020-06-18 2021-11-23 江苏卓高新材料科技有限公司 一种水性粘结剂、其制备方法、及应用
CN117293314B (zh) * 2023-09-25 2024-04-12 浙江煌能新能源科技有限公司 一种提高硅基负极电性能的粘接剂、电池负极及用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09227172A (ja) * 1996-02-20 1997-09-02 Dai Ichi Kogyo Seiyaku Co Ltd ガラス繊維用集束剤
CN101235107A (zh) * 2007-12-29 2008-08-06 天津市职业大学 用亚硫酸氢钠处理游离醛制备环保型胶粘剂的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1209433C (zh) * 2001-06-12 2005-07-06 成都茵地乐电源科技有限公司 锂离子电池水性粘合剂制备方法
CN101260282B (zh) * 2008-03-18 2010-08-11 成都中科来方能源科技有限公司 锂离子电池用水性粘合剂、制备方法及锂离子电池正极片
KR101519979B1 (ko) * 2013-03-25 2015-05-20 한국세라믹기술원 리튬이온이차전지용 음극 조성물
CN104448158B (zh) * 2014-12-05 2017-08-04 北京蓝海黑石科技有限公司 一种锂电池用水性粘合剂的制备方法
CN105261759A (zh) * 2015-09-22 2016-01-20 深圳市贝特瑞新能源材料股份有限公司 一种锂电池用水性粘结剂及其制备方法、锂电池极片

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09227172A (ja) * 1996-02-20 1997-09-02 Dai Ichi Kogyo Seiyaku Co Ltd ガラス繊維用集束剤
CN101235107A (zh) * 2007-12-29 2008-08-06 天津市职业大学 用亚硫酸氢钠处理游离醛制备环保型胶粘剂的方法

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020090927A1 (fr) * 2018-10-31 2020-05-07 日本ゼオン株式会社 Composition de liant pour batterie secondaire et son procédé de fabrication, composition de bouillie pour batterie secondaire, couche fonctionnelle pour batterie secondaire et son procédé de fabrication, couche d'électrode pour batterie secondaire et batterie secondaire
CN113169334A (zh) * 2018-10-31 2021-07-23 日本瑞翁株式会社 二次电池用浆料组合物、电极层、粘结剂组合物和功能层及二者的制造方法、以及二次电池
JPWO2020090927A1 (ja) * 2018-10-31 2021-09-24 日本ゼオン株式会社 二次電池用バインダー組成物およびその製造方法、二次電池用スラリー組成物、二次電池用機能層およびその製造方法、二次電池用電極層、並びに二次電池
JP7468352B2 (ja) 2018-10-31 2024-04-16 日本ゼオン株式会社 二次電池用バインダー組成物およびその製造方法、二次電池用スラリー組成物、二次電池用機能層およびその製造方法、二次電池用電極層、並びに二次電池
CN113169334B (zh) * 2018-10-31 2024-09-10 日本瑞翁株式会社 二次电池用浆料组合物、电极层、粘结剂组合物和功能层及二者的制造方法、以及二次电池
CN115053376A (zh) * 2020-03-11 2022-09-13 宁德新能源科技有限公司 锂离子电池及电子装置
CN111668489A (zh) * 2020-06-17 2020-09-15 上海洛法化工有限公司 一种混合型锂离子电池硅负极水系粘结剂及其制备工艺
CN116315032A (zh) * 2021-12-20 2023-06-23 比亚迪股份有限公司 一种锂离子电池及其制备方法及动力车辆
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

Also Published As

Publication number Publication date
CN105958075B (zh) 2018-09-28
CN105958075A (zh) 2016-09-21

Similar Documents

Publication Publication Date Title
CN105958075B (zh) 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
US10882990B2 (en) Multi-functionally modified polymer binder for lithium ion batteries and use thereof in electrochemical energy storage devices
CN107793967B (zh) 一种锂离子电池交联型水性粘结剂的制备方法
WO2023005520A1 (fr) Liant, son procédé de préparation et son utilisation
CN109957360A (zh) 一种水性粘结剂及二次电池
CN103326027A (zh) 一种锂离子电池负极及锂离子电池
CN108933260A (zh) 水溶性电极粘结剂、电极片及其制备方法以及电化学储能装置
JP2020017504A (ja) リチウムイオン電池電極用スラリー及びその製造方法、リチウムイオン電池用電極、並びにリチウムイオン電池
WO2025167067A1 (fr) Liant soluble dans l'eau, feuille d'électrode de batterie et son utilisation
KR101227152B1 (ko) 전극의 도전성 접착층 형성용 조성물, 이를 사용한 전극의 제조 방법 및 전극
CN109957361B (zh) 一种水性粘结剂及二次电池
CN110690451A (zh) 一种锂离子电池用导电水性粘合剂及其制备方法和应用
JP2019110002A (ja) リチウムイオン電池用バインダー水溶液、リチウムイオン電池用電極スラリー及びその製造方法、リチウムイオン電池用電極、並びにリチウムイオン電池
WO2024000560A1 (fr) Pâte conductrice, collecteur de courant, batterie secondaire, module de batterie, bloc-batterie et appareil électrique
CN113429927B (zh) 一种聚酰亚胺粘结剂及其制备方法、硅碳负极片
CN102117914A (zh) 一种电池水系粘结剂及使用该粘结剂的电极及电池
CN108832129A (zh) 一种电极浆料及制备方法及由其制成的锂离子电池电极
WO2023004633A1 (fr) Batterie, module de batterie, bloc-batterie et dispositif électrique
CN110492101B (zh) 一种锂离子电池负极粘结剂及其制备方法和应用
CN115939398B (zh) 一种导电粘结剂、制备方法及其应用
CN117038983A (zh) 一种锂离子电池粘结剂的制备方法及应用
CN117143547A (zh) 粘结剂及其制备方法、负极极片、电池和用电装置
CN116565200A (zh) 锂离子电池正极浆料用添加剂及其制备方法和应用
CN116478641B (zh) 一种强粘附型粘合剂及其制备方法和应用
CN114361456B (zh) 一种锂电池用水性功能化导离子粘结剂、制备方法及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16906975

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16906975

Country of ref document: EP

Kind code of ref document: A1