CN114891136B - Multi-branched structure binder and preparation method and application thereof - Google Patents

Multi-branched structure binder and preparation method and application thereof Download PDF

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CN114891136B
CN114891136B CN202210648668.1A CN202210648668A CN114891136B CN 114891136 B CN114891136 B CN 114891136B CN 202210648668 A CN202210648668 A CN 202210648668A CN 114891136 B CN114891136 B CN 114891136B
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silicon
binder
application
paa
hours
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CN114891136A (en
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王保峰
沈军
毛益阳
王仁馨
胡莹莹
王瑞琳
张惠惠
胡露露
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Shanghai Electric Power University
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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
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application discloses a multi-branched structure binder, a preparation method and application thereof. The grafting modified adhesive prepared by the application provides more active sites, and can generate multidimensional bonding action with silicon particles, thereby improving bonding strength, maintaining the structural integrity of an electrode and improving the cycle performance of a battery; meanwhile, the adhesive can form a covalent bond on the surface of the nano silicon particles, has higher strength, can inhibit the volume expansion of the silicon negative electrode, and can greatly improve the electrochemical performance of the silicon negative electrode of the lithium ion battery.

Description

Multi-branched structure binder and preparation method and application thereof
Technical Field
The application belongs to the technical field of chemical power supplies, and particularly relates to a multi-branched structure binder, and a preparation method and application thereof.
Background
Lithium ion batteries are outstanding in the vision of people due to the advantages of high capacity, no memory effect, rapid and reversible charge and discharge, high coulombic efficiency and the like. With the increasing requirements of 3C electronic products and electric automobiles on the capacity and service life of lithium ion batteries, the conventional cathode material graphite for market business cannot meet the requirement of high capacity. People are beginning to focus their eyes on some new high capacity electrode materials.
Silicon can achieve up to 5 silicon stores 22 lithium (Li 22 Si 5 ) The theoretical specific capacity is 4200mAh/g, the storage is rich, the cost is low, and therefore the silicon material is considered as one of the anode materials with the most application prospect of the next generation of high-energy density lithium ion batteries. Silicon is combined with lithium through alloying reaction to obtain extremely high capacity, so that co-intercalation of electrolyte solvent does not occur in the intercalation and deintercalation process of lithium ions, and the method has wider selection range of electrolyte. In addition, silicon has higher deintercalation potential than a carbon material, so that the lithium separation can be reduced or even avoided during charging and discharging at a high multiplying power, the formation of lithium dendrites is avoided, and the safety of the battery is improved.
However, silicon electrodes currently have the major drawbacks of poor intrinsic conductivity and large volume expansion during charge and discharge. Among them, the volume expansion of silicon can lead to rapid decay of electrode performance, and the main decay mechanism mainly has three aspects: first, the repeated volume changes of the silicon cause particle-to-particle loosening between the particles and the current collector, resulting in loss of electrical contact of the silicon particles and detachment of the electrode body from the current collector. Second, repeated volume changes of silicon destroy the original solid electrolyte interface layer (SEI), so that silicon particles are in direct contact with electrolyte, and an unstable thick SEI film is formed. This process continues to consume lithium ions and electrolyte, thereby reducing the coulombic efficiency per cycle, ultimately depleting the electrolyte. Third, most of the silicon particles are crushed by being unable to withstand the stress generated by the volume expansion. These crushed silicon particles are dispersed to cause electrical isolation, and at the same time, further growth of the SEI film is caused due to an increase in surface area. Thus, research on silicon electrodes is now focused mainly on how to solve the volume expansion of silicon.
At present, most of measures adopted for the volumetric effect of silicon are nano-crystallization of silicon materials, hollow and porous structuring of silicon particles, or carbon-silicon composite materials with special structures (WangX, zhang Y, maL, et al, acta Chimica Sinica,2019,77 (1): 24-40), and although the measures have certain effects on material modification, the preparation conditions are severe and cannot be applied to practical use due to complicated preparation processes. In practical applications, the binder is one of the essential non-electrochemically active components in the electrode, and in addition to ensuring particle-to-particle connection, can also maintain intimate contact between the electrode and the current collector to prevent the electrode from falling off the current collector. The polymer binder plays a very important role in the formation of the SEI film and in maintaining the mechanical integrity of the electrode and the integrity of the conductive network. In addition, due to the volumetric effect, silicon requires a suitable binder to buffer, and even constrain the volumetric expansion of, the silicon as compared to other electrode materials. The traditional PVDF and the common water-soluble binders (PAA, CMC, PVA and the like) are difficult to bear huge volume expansion, so that the electrochemical performance of the silicon electrode is poor, and a plurality of modification works on the binders are carried out by researchers at home and abroad, but the synthesis of most of the modified binders involves polymerization reaction, the reaction condition is complex, the reaction process is complex, and the commercialization is difficult. Therefore, the development of a novel binder with simple synthesis, strong adhesion and good mechanical properties is very important for the development of silicon-based cathodes.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The present application has been made in view of the above and/or problems occurring in the prior art.
Therefore, the application aims to overcome the defects in the prior art and provide a preparation method of the multi-branched structure binder.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
preparing a precursor: adding polyacrylic acid into deionized water, magnetically stirring, adding a grafting modifier, continuously stirring and heating to obtain a uniformly mixed precursor;
preparing a multi-branched structure binder: and (3) reacting the precursor under the conditions of vacuum and high temperature, swelling after the reaction is finished, and freeze-drying to obtain the multi-branched structure binder.
As a preferred embodiment of the present application, wherein: the grafting modifier is one or more of glycine, glutamic acid, taurine and citric acid.
As a preferred embodiment of the present application, wherein: the mass ratio of the polyacrylic acid to the grafting modifier is 1:0.05 to 0.2 part of the mixture of the polyacrylic acid and the grafting modifier, wherein the mixture of the polyacrylic acid and the grafting modifier is 0 to 50 parts of the mixture of the polyacrylic acid and the grafting modifier, based on the mass parts of the adhesive.
As a preferred embodiment of the present application, wherein: the precursor is prepared, wherein the heating temperature is 100-180 ℃, and the heating time is 2-12 h.
As a preferred embodiment of the present application, wherein: the preparation method of the multi-branched structure binder comprises the steps of preparing the multi-branched structure binder, wherein the swelling time is 1-4 h, and the freeze drying time is 24-48 h.
Another object of the present application is to overcome the deficiencies of the prior art by providing a multi-branched structural adhesive.
It is a further object of the present application to overcome the deficiencies of the prior art and to provide the use of a multi-branched structured adhesive.
In order to solve the technical problems, the application provides the following technical scheme: comprising the steps of (a) a step of,
and coating a material containing an active material, a conductive agent, a multi-branched structure binder and water on a current collector, drying to obtain a negative plate, and applying the obtained negative plate to a lithium ion battery.
As a preferred embodiment of the present application, wherein: the active material is nano silicon, and the conductive agent is one or more of super P and acetylene black.
As a preferred embodiment of the present application, wherein: the binder is 10-20 parts by mass of the negative electrode sheet.
As a preferred embodiment of the present application, wherein: and the drying is carried out, wherein the temperature is 100-180 ℃ and the time is 8-12 h.
The application has the beneficial effects that:
(1) The branched PAA binder disclosed by the application has excellent electrochemical performance as a lithium ion silicon-based negative electrode binder, and because of the multi-branched structure, grafted molecules contain a plurality of functional groups and can be bonded with the surface of silicon in a multi-dimensional way, so that the cohesiveness with silicon is improved, the volume expansion of the silicon is effectively relieved, the structural integrity of an electrode is maintained, and the method support is provided for the research and application of the lithium ion battery silicon negative electrode binder in the future.
(2) The preparation process is simple, the modified binder with the multi-branched structure is generated by a grafting method, the prepared branched PAA binder is easy to dissolve in water, exists in a hydrogel form, has the characteristic of environmental friendliness, can be produced in large scale, and has no pollution.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a FTIR spectrum of the binder prepared in example 1 of the present application.
FIG. 2 is a graph of 180 degree peel test of the adhesive made in example 1 of the present application.
FIG. 3 is a CV curve of the adhesive prepared in example 1 of the present application.
FIG. 4 is a graph showing the cycle performance of the adhesive prepared in example 1 of the present application.
FIG. 5 is a graph showing the rate performance of the adhesive prepared in example 1 of the present application.
FIG. 6 is an SEM image of the adhesive prepared in example 1 of the application.
Fig. 7 is an initial SEM image of the electrode sheet of the binder prepared in example 1 of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Adding 1g of polyacrylic acid (PAA) into 4.725mL of deionized water, magnetically stirring, adding 0.05g of citric acid water, heating to 60 ℃, and maintaining at the temperature for 3 hours to form a uniformly mixed precursor;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder CA-g-PAA.
Example 2
Adding 1g of polyacrylic acid (PAA) into 4.95mL of deionized water, magnetically stirring, adding 0.1g of citric acid water, heating to 60 ℃, and maintaining at the temperature for 3 hours to form a uniformly mixed precursor;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder CA-g-PAA.
Example 3
Adding 1g of polyacrylic acid (PAA) into 5.4mL of deionized water, magnetically stirring, adding 0.15g of citric acid water, heating to 60 ℃, and maintaining at the temperature for 3 hours to form a uniformly mixed precursor;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder CA-g-PAA.
Example 4
Adding 1g of polyacrylic acid (PAA) into 5.85mL of deionized water, magnetically stirring, adding 0.2g of citric acid water, heating to 60 ℃, and maintaining at the temperature for 3 hours to form a uniformly mixed precursor;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder CA-g-PAA.
Comparative example 1
Adding 1g of polyacrylic acid (PAA) into 5.4mL of deionized water, magnetically stirring, adding 0.15g of glycine, heating to 60 ℃ in a water bath, and maintaining at the temperature for 3 hours to form a uniformly mixed precursor;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder.
Comparative example 2
Adding 1g of polyacrylic acid (PAA) into 5.4mL of deionized water, magnetically stirring, adding 0.15g of glutamic acid, heating to 60 ℃ in a water bath, and then maintaining at the temperature for 3 hours to form a precursor which is uniformly mixed;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder.
Comparative example 3
Adding 1g of polyacrylic acid (PAA) into 5.4mL of deionized water, magnetically stirring, adding 0.15g of taurine, heating to 60 ℃ in a water bath, and then maintaining at the temperature for 3 hours to form a precursor which is uniformly mixed;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum condition, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the modified binder.
Example 5
Electrochemical performance test:
uniformly mixing nano silicon (anode material), acetylene black (conductive carbon) and CA-g-PAA (binder) synthesized by the method of the embodiment and the comparative example according to the mass ratio of 6:2:2, coating the mixture on copper foil, drying the mixture in a vacuum oven at 150 ℃ for 8 hours, and pressing the dried mixture into wafers with the diameter of 14 mm.
The preparation of the lithium ion battery adopts the conventional means in the field, namely, the metal lithium is used as a counter electrode; liPF at 1mol/L 6 EC: DMC: EMC (V: V=1:1:1) is taken as a base electrolyte, an additive is FEC, and the mass ratio of the additive in the electrolyte is 0-10wt%; and assembling the button cell in a glove box protected by argon atmosphere. Electrochemical performance test is carried out by adopting a battery tester of Shenzhen New wile electronics Limited company, and the charge-discharge voltage range is 0.01V-1.5V (vs. Li) + Li) at a test temperature of 25 ℃. Meanwhile, impedance test is carried out by adopting a CHI660E type electrochemical workstation of Shanghai Chenhua limited company, and the test frequency is 0.01-100000 Hz.
Table 1 shows electrochemical performance tables of the lithium ion battery negative electrode sheets prepared in examples 1 to 4 and comparative examples 1 to 3;
TABLE 1
As can be seen from Table 1, when the adhesive prepared by the application is applied to a silicon anode of a lithium ion battery, the adhesive has better mechanical property and electrochemical property, because the adhesive prepared by the application has a multi-branched structure, and because the adhesive has a plurality of branched chains, groups (such as sulfonic acid groups, carboxylic acid groups and the like) on the branched chains and carboxylic acid groups on the PAA main chain can be bonded with silicon to form chemical bonds, thereby generating multidimensional bonding effect, firmly grabbing silicon particles, and relieving pulverization of silicon in the process of volume expansion and contraction of silicon, thereby better maintaining the structural integrity of the electrode.
According to the application, the influence of different grafting degrees on electrochemistry can be explored by controlling the amount of different grafting modifiers, so that proper grafting modifiers and the use amount are selected, and the mass ratio of the grafting modifiers to the polyacrylic acid is 0.1: the technical effect achieved in the step 1 is best.
In addition, the taurine grafted and modified adhesive shows better electrochemical performance under the same grafting degree; by using different modifier binders for testing, the influence of different grafting modifiers on the electrochemical performance of PAA can be explored, and then a proper grafting modifier is selected, so that the service life of the lithium ion silicon-based negative electrode battery is effectively prolonged.
FIG. 1 is a FTIR spectrum of the prepared CA-g-PAA, from which it is seen that the characteristic peak of C=O bond on carboxyl group of PAA appears at 1700cm -1 At this point, but after modification with citric acid, shift to 1707cm in the CA-g-PAA spectrum -1 This demonstrates that the carboxyl group on part of PAA successfully forms a bond with the hydroxyl group on citric acid, forming an ester group, proving the synthesis of the target product.
Fig. 2 is a graph of 180 ° peel test of the negative electrode sheet using CA-g-PAA and PAA as binders, and it is understood that the average peel strength of the non-recycled silicon electrode containing CA-g-PAA binder is 4.07N, and the average peel strength of the PAA binder is only 1.36N. The results show that CA-g-PAA adhesives have higher adhesive power than PAA adhesives.
Fig. 3 is a cyclic voltammogram of a button cell prepared from the above-described negative electrode, and a redox peak is clearly observed, indicating that the modified binder has no effect on electrochemical behavior. At the same time, the peak current of the redox peak gradually increases from the first to the fifth turn of the scan, indicating that the electrode material is a gradual activation process during the initial electrochemical reaction.
Fig. 4 is a graph showing charge-discharge cycle performance of the button cell prepared by the above-described negative electrode. As can be seen, at 840mA g -1 The capacity of the silicon electrode composed of the PAA binder grafted by citric acid after 100 times circulation is 2627.4mAh g under the current density -1 While the capacity of the silicon electrode composed of the PAA binder is only 942.3mAh g -1 The material has better cycle performance.
FIG. 5 is a graph showing the rate performance of the above-described button cell at various current densities, and the prepared cell exhibits specific discharge capacities of 3596, 3189, 2744, 2023 and 1499mAh g when the prepared cell is subjected to charge-discharge tests at current densities of 0.1C, 0.2C, 0.3C, 0.5C and 1C, respectively -1 . The specific discharge capacity was maintained at 2897mAh g even when the current density was restored to 0.2C -1 The adhesive has higher specific capacity and excellent rate capability when being used for the silicon negative electrode of the lithium ion battery.
Fig. 6 is an SEM image of the negative electrode sheet using CA-g-PAA and PAA as binders, as shown by the figure, all electrodes had no significant difference before cycling and had a flat surface morphology. After 5 cycles, micron-sized cracks were observed on the surface of the PAA/Si electrode, whereas no obvious cracks were found on the CA-g-PAA/Si electrode, indicating that the modified binder well maintained the structural integrity of the electrode.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.

Claims (1)

1. A preparation method of a multi-branched structure binder is characterized by comprising the following steps: comprising the steps of (a) a step of,
adding 1g of polyacrylic acid into 4.95mL of deionized water, magnetically stirring, adding 0.1g of citric acid water, heating to 60 ℃, and maintaining at the temperature for 3 hours to form a uniformly mixed precursor;
and (3) reacting the precursor for 8 hours at the temperature of 150 ℃ under vacuum, naturally cooling, and then adding deionized water into the reaction product to swell for 2 hours to obtain the multi-branched structure binder.
CN202210648668.1A 2022-06-09 2022-06-09 Multi-branched structure binder and preparation method and application thereof Active CN114891136B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105504169A (en) * 2016-01-07 2016-04-20 上海交通大学 Adhesive for lithium ion battery
CN110323445A (en) * 2019-06-25 2019-10-11 西安交通大学苏州研究院 PAA-CA complex phase binder and preparation method thereof
CN111430712A (en) * 2020-03-31 2020-07-17 上海电力大学 Preparation method of novel silicon-based negative electrode binder of lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105504169A (en) * 2016-01-07 2016-04-20 上海交通大学 Adhesive for lithium ion battery
CN110323445A (en) * 2019-06-25 2019-10-11 西安交通大学苏州研究院 PAA-CA complex phase binder and preparation method thereof
CN111430712A (en) * 2020-03-31 2020-07-17 上海电力大学 Preparation method of novel silicon-based negative electrode binder of lithium ion battery

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