CN109957360B - Water-based binder and secondary battery - Google Patents

Water-based binder and secondary battery Download PDF

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CN109957360B
CN109957360B CN201711405497.5A CN201711405497A CN109957360B CN 109957360 B CN109957360 B CN 109957360B CN 201711405497 A CN201711405497 A CN 201711405497A CN 109957360 B CN109957360 B CN 109957360B
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binder
formula
negative electrode
pole piece
secondary battery
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CN109957360A (en
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吴博
王龙
郑义
钟泽
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Contemporary Amperex Technology Co Ltd
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides
    • 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
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Polymers & Plastics (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses an aqueous binder and a secondary battery. The adhesive has self-repairing capability and is a polymer containing at least two monomer units, wherein one monomer contains both a sulfonic acid group and an amide group, and the other monomer contains an alcohol ester group or/and a carboxylic acid ester group. The number average molecular weight of the polymer is preferably 20 ten thousand or more. The invention also relates to a secondary battery, which comprises a positive pole piece, a negative pole piece, a separation film and electrolyte, wherein at least one of the positive pole piece, the negative pole piece and the separation film (preferably the negative pole piece) contains the binder. Compared with the binder in the prior art, the binder provided by the invention has the advantages of high electrochemical stability, strong binding capacity and good mechanical property, and can be used for remarkably prolonging the cycle life of a secondary battery and reducing the cycle expansion. Therefore, the binder material has good application prospect in secondary batteries.

Description

Water-based binder and secondary battery
Technical Field
The present invention relates to the technical field of secondary batteries, and particularly to an aqueous binder for secondary batteries and a secondary battery containing the same.
Background
Since its birth, secondary batteries have been used in many fields. From the application field of the secondary battery at present, the secondary battery not only can be widely applied to electronic products such as mobile phones, chargers and the like, but also can make a certain breakthrough in the fields of vehicle-mounted power supplies, energy storage systems and the like. Most of the current negative electrode materials of commercial secondary batteries are graphite or various carbon materials synthesized by taking graphite as a precursor, the theoretical lithium storage capacity (372mAh/g) of the negative electrode materials reaches the limit, and the requirements of the power batteries on high energy density cannot be met from the viewpoint of the requirements of the power batteries. The highest specific capacity of the next-generation silicon-based negative electrode material can reach 4200mAh/g, but the silicon material can generate a huge volume effect (400%) under the condition of high lithium desorption, so that the electrode material loses a conductive network due to the collapse of an electrode structure and the peeling of the electrode material, and the capacity of the electrode is rapidly attenuated, and the cycle performance is poor. Therefore, the development of a negative electrode tab with high energy density and high adhesion performance becomes a technical bottleneck for developing the next generation of advanced secondary batteries.
The binder is an important component of the secondary battery, and plays a role in maintaining the structural integrity of the electrode and ensuring the normal and repeated operation of the battery in the charging and discharging processes.
One binder currently used for negative electrode materials is mainly classified into: sodium carboxymethylcellulose (CMCNa) is matched with styrene butadiene rubber emulsion (SBR) or propyl benzene rubber emulsion (SAR), wherein the CMCNa plays a role in dispersing active substances and stabilizing slurry, and the SBR or SAR emulsion plays a role in bonding active substance particles and particles with a substrate. Although SBR has certain adhesiveness and elasticity, it is in point contact connection between active material particles and between particles and a current collector, and has weak binding ability and poor reversible recovery mechanical properties.
The other existing binder for the negative electrode material is a polysaccharide material, such as sodium alginate, cyclodextrin, chitosan and the like, which has low mechanical strength, limited effect of inhibiting the expansion of the graphite negative electrode and the silicon-based negative electrode in the charge and discharge processes and risk of cyclic demoulding.
Modified polyacrylic acid (PAA) materials can also be used as binders of negative electrode materials, but the PAA materials can react with ions in the process of electrode de-intercalation to cause capacity loss and first coulombic efficiency reduction, and the PAA materials have poor fatigue resistance and poor electrolyte wettability to cause poor dynamic performance of the negative electrode.
Therefore, in order to obtain a secondary battery having excellent cycle performance, high dynamic performance, and high energy density, development of a suitable binder is urgently required.
The invention is specially provided for overcoming the defects in the prior art.
Disclosure of Invention
An object of the present invention is to provide a binder for secondary batteries having high adhesiveness and fatigue resistance.
It is another object of the present invention to provide a secondary battery having good properties, particularly cycle performance, kinetic performance and high energy density.
In one aspect, the present invention provides an aqueous binder which is a polymer comprising at least two monomer units, wherein one monomer unit is a unit represented by formula (I) comprising both a sulfonic acid group and an amide group, and the other monomer unit is a unit selected from the group consisting of units represented by formula (II) -1 or formula (II) -2,
Figure BDA0001520257950000021
wherein,
in the formula (I), R1Selected from H, straight chain or branched chain alkyl with 1,2, 3, 4, 5 or 6 carbon atoms, CnH2nIs a straight or branched chain alkylene group with n being 1,2, 3, 4, 5, 6, 7 or 8, and X is selected from hydrogen ion, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion or ammonium ion;
in the structural formula (II) -1, R1Selected from H, straight chain or branched chain alkyl with 1,2, 3, 4, 5 or 6 carbon atoms, R2Selected from H, benzoyl, straight or branched chain alkanoyl with total number of carbon atoms of 1,2, 3, 4, 5, 6, 7 or 8;
in the formula (II) -2R1Selected from H, straight chain or branched chain alkyl with 1,2, 3, 4, 5 or 6 carbon atoms, R3Selected from H, phenyl, benzyl, straight chain or branched chain alkyl with 1,2, 3, 4, 5, 6, 7 or 8 carbon atoms;
r in the formula (I)1With R in the formula (II) -11R in the structural formula (II) -21Are each independently selected.
The structural formula (I) unit as the first component accounts for 40 to 90 mol%, preferably 50 to 80 mol% of the binder, and the best self-healing effect of the binder can be achieved when the mol% of the structural formula (I) is within this range. The units of the formula (II) -1 and/or the units of the formula (II) -2 as a second component represent(s) from 10 to 60, preferably from 20 to 50, mol% of the binder (when both units of the formula (II) -1 and (II) -2 are present in the binder, the sum of the mol% of the units is from 10 to 60, preferably from 20 to 50%). Preferably, a structural unit having the structure of formula (II) -1 is used. When the mole percentage of each unit of the binder is within the above range, the adhesiveness of the binder is optimal.
Preferably, the number average molecular weight of the binder is 20 ten thousand or more, preferably 20 ten thousand to 150 ten thousand, and more preferably 40 ten thousand to 110 ten thousand.
It will be understood by those skilled in the art that the binder of the present invention may contain, in addition to the unit of formula (I), the unit of formula (II) -1 or (II) -2, other kinds of units as necessary, as long as they are copolymerizable with the unit of formula (I), the unit of formula (II) -1 or (II) -2 without adversely affecting the properties of the binder. The molar percentage of other types of structural units in the binder is generally between 0 and 10%.
In some preferred embodiments of the present invention, the binder of the present invention contains no other kind of structural unit other than the structural formula (I) unit, the structural formula (II) -1 unit or the (II) -2 unit. In this case, the binder of the present invention is composed of the unit of structural formula (I) and the unit of structural formula (II) -1 and/or the unit of structural formula (II) -2, and may be composed of the unit of structural formula (I) and the unit of structural formula (II) -1, the unit of structural formula (I) and the unit of structural formula (II) -2, or the unit of structural formula (I), the unit of structural formula (II) -1 and the unit of structural formula (II) -2. In the case where the binder of the present invention is a terpolymer as described above, the sum of the molar percentages of both the units of formula (II) -1 and of the units of formula (II) -2 satisfies the condition specified above, i.e. represents from 10% to 60%, preferably from 20% to 50%, of the molar percentage of the binder.
In some preferred embodiments, in structural formula (I), R1Is selected from H or C1-4Straight or branched alkyl (especially CH)3)，CnH2nIs n ═ 1 to 6 (more preferably n ═ 1 to 4)Is straight-chain or branched alkylene, X is selected from H+、Li+、Na+、K+、NH4 +。
Specific examples of units of formula (I) include, but are not limited to, a poly (sodium 2-acrylamido-2-methylpropanesulfonate) segment, a poly (3-methacrylamido-2-methyl-1-propanesulfonic acid) segment, a poly (lithium 3-acrylamido-2, 2-dimethyl-1-propanesulfonate) segment, a poly (ammonium 3-acrylamido-1-propanesulfonate) segment, a poly (potassium 3-methacrylamido-2, 3-dimethyl-2-butanesulfonate) segment.
In some preferred embodiments, in structural formula (II) -1, R1Is selected from H or C1-4Straight or branched alkyl (especially CH)3)，R2Selected from H, benzoyl, C unsubstituted by substituents1-6Straight or branched alkanoyl (especially C unsubstituted with substituent)1-4A straight or branched alkanoyl group).
Specific examples of the unit of formula (II) -1 include, but are not limited to, a polyvinyl alcohol segment, a polyvinyl acetate segment, a polyvinyl benzoate segment, a polyvinyl propionate segment, or a polyvinyl n-butyrate segment.
In some preferred embodiments, in structural formula (II) -2, R1Is selected from H or C1-4Straight or branched alkyl (especially CH)3)，R3Selected from H, phenyl, C unsubstituted by substituents1-8(more preferably C)1-6Most preferably C1-4) Linear or branched alkyl.
Specific examples of the unit of formula (II) -2 include, but are not limited to, a polyacrylic acid fragment, a polymethyl methacrylate fragment, a polyethyl methacrylate fragment, a polypropyl methacrylate fragment, a polyisopropyl methacrylate fragment, a poly-n-butyl acrylate fragment, or a polyisopentyl methacrylate fragment.
The term "alkyl" as used herein has the meaning commonly understood in the art and refers to a saturated hydrocarbon consisting of only two elements, C and H, which forms a radical after any carbon atom has lost one hydrogen atom. As used herein, "alkyl" includesStraight chain alkyl and branched chain alkyl. The alkyl group may be unsubstituted or substituted, but is preferably unsubstituted. When alkyl is substituted, the number of substituents may be, for example, 1 to 3, each substituent may be, for example, independently selected from hydroxy, halogen, nitro, cyano, amino, carboxy, C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, ═ O, ═ S, SH, CF3Etc.; preferred substituents are halogen, C1-4Alkyl, or C1-4An alkoxy group. Examples of "alkyl" as used herein include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, chloromethyl, fluoroethyl, trifluoromethyl or 1,1, 1-trifluoroethyl, and the like.
The term "alkylene" as used herein refers to a divalent group derived from a straight-chain or branched-chain saturated hydrocarbon by removing two hydrogen atoms, for example, methylene, 1, 2-ethylene, 1, 3-propylene, 1, 4-butylene, 1, 5-pentylene, 1, 6-hexylene, 2-dimethylpropylene, and the like. The alkylene group of the present invention may be unsubstituted or substituted, but is preferably unsubstituted. When the alkylene group is substituted, the number of substituents may be, for example, 1 to 3, and each substituent may be, for example, independently selected from the group consisting of hydroxy, halogen, nitro, cyano, amino, carboxy, C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, ═ O, ═ S, SH, CF3Etc.; preferred substituents are halogen, C1-4Alkyl, or C1-4An alkoxy group.
The term "alkanoyl" as used herein refers to R- (C ═ O) -, where R is alkyl. Examples of "alkanoyl" include, but are not limited to, formyl, acetyl, propionyl, isobutyryl, oxalyl, and the like. Alkanoyl may be unsubstituted or optionally substituted with 1-3 substituents, wherein each substituent may be independently selected from hydroxy, halogen, nitro, cyano, amino, carboxy, C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, ═ O, ═ S, SH, CF3Etc.; preferred substituents are halogen, C1-4Alkyl, or C1-4An alkoxy group.
The term "benzoyl" as used herein means C6H5- (C ═ O) -. The benzoyl group may be unsubstituted or optionally substituted with 1 to 3 substituents, wherein each substituent may be independently selected from hydroxy, halogen, nitro, cyano, amino, carboxy, C1-6Alkyl radical, C1-6Alkoxy radical, C3-6Cycloalkyl, ═ O, ═ S, SH, CF3Etc.; preferred substituents are halogen, C1-4Alkyl, or C1-4An alkoxy group.
All references herein to numerical ranges of numbers of carbon atoms, such as "number of carbon atoms from 1 to 6", "C1-6”、“CnH2n… … "for n being 1-8, refers to the enumeration of all positive integers in the upper and lower range. For example, "the number of carbon atoms is 1 to 6" means "the number of carbon atoms is 1,2, 3, 4, 5, 6", "C1-6"represents" C1、C2、C3、C4、C5、C6”，“n＝1-8”、“C3-6The expressions "and the like have similar meanings. Likewise, where a numerical range refers to the number of substituents, it also refers to an enumeration of all positive integers within its upper and lower limits, e.g. "1-3 substituents" and "the number of substituents may be, for example, 1 to 3", each denoting 1,2 or 3 substituents.
The binder polymer of the present invention has a simple structure, and can be easily prepared by those skilled in the art according to its structure, for example, by the most common solution polymerization method. The preparation process is simple, easy to control, high in feasibility, less in environmental pollution and suitable for industrial mass production. Specifically, the binder of the present invention can be prepared by the following method: mixing a vinyl unsaturated amide sulfonic acid monomer (used for forming a monomer unit with a structural formula (I)), a vinyl unsaturated ester monomer (used for forming a monomer unit with a structural formula (II) -1 or a monomer unit with a structural formula (II) -2) and an optional polymerization initiator, continuously and slowly dripping the mixture into a solvent under an inert gas atmosphere, and carrying out polymerization reaction at a certain temperature and time to prepare the binder. Wherein, the polymerization temperature and the polymerization time can directly influence the molecular weight of the binder, preferably, the polymerization temperature is controlled to be 60-120 ℃, and the polymerization reaction time is controlled to be 6-24 h; more preferably, the polymerization temperature is controlled to be 80-100 ℃, and the polymerization reaction time is controlled to be 8-20 h.
Wherein the solvent can be a mixture of at least one of tetrahydrofuran, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, dioxane, acetone and acetonitrile and water, and the ratio of the mass of the solvent to the sum of the mass of the vinyl unsaturated amide sulfonic acid monomer and the mass of the vinyl unsaturated ester monomer can be 100 (50-200).
The feeding molar ratio of the vinyl unsaturated amide sulfonic acid monomer to the vinyl unsaturated ester monomer is preferably 3:1 to 12:1, and the obtained adhesive has good water solubility and stability and optimal adhesive property and crosslinking property.
Among the optional polymerization initiators are, for example, azobisisobutyronitrile, benzoyl peroxide, 4' -azobis (4-cyanovaleric acid), most preferably azobisisobutyronitrile. The mass of the polymerization initiator is 0.1-3% of the sum of the mass of the vinyl unsaturated amide sulfonic acid monomer and the mass of the vinyl unsaturated ester monomer, and the mass of the polymerization initiator is most preferably 0.5-2%. The inert gas is argon or nitrogen, most preferably argon.
The adhesive is prepared by adopting the solvent system, the preferable polymerization initiator, the preferable proportion and the preferable polymerization atmosphere, temperature and time, and the molecular weight range can be controlled within the preferable range of 20-150 ten thousand due to the proper type and proportion of the initiator and mild reaction conditions.
The adhesive can be used as an adhesive for a positive pole piece, a negative pole piece or an isolating membrane of a secondary battery. The binder of the present invention is particularly preferable as a binder of a negative electrode tab of a secondary battery, because problems caused by the binding of the negative electrode tab in the secondary battery are more significant.
The adhesive is an ionic waterborne polymer, wherein a structural unit side chain simultaneously contains an amide group and a sulfonic acid group, and O in the sulfonic acid group (-S ═ O-) can form strong hydrogen bond action with H in the amide group (N-H), so that a three-dimensional hydrogen bond network structure is formed among polymer molecular chains. When the negative active material causes larger volume expansion or shrinkage change due to charge and discharge, the binder material still has excellent adhesion and mechanical strength, and even if the microscopic interface of the material is fractured due to repeated volume expansion, hydrogen bond self-repairing damaged parts (namely self-healing) can be quickly formed by the contact between the interfaces after the material shrinks, so that the fatigue resistance of the binder material is further improved, and the problems of binder peeling and conductive network damage caused by the deterioration or failure of the adhesion performance of the binder due to the volume change of the negative electrode are solved.
In addition, as the side chain of the material contains a sulfonic group structure, compared with the traditional sodium carboxymethyl cellulose and polyacrylic acid binder materials, the acidity of the sulfonic group is stronger than that of the carboxylic group, and the stronger charge delocalization effect of the material enables counter ions paired with the sulfonic group to have lower dissociation energy. Therefore, the ionic conduction performance is good, the mobility is high, and the polarization condition is effectively reduced. Therefore, the problems of low lithium ion conductivity and poor dynamic performance of the conventional styrene-butadiene rubber emulsion, styrene-acrylic rubber emulsion, sodium carboxymethylcellulose and polyacrylic acid aqueous negative electrode binder, and particularly the problem of rapid battery capacity attenuation caused by high-rate charge and discharge are effectively solved.
The other structural unit of the adhesive contains alcohol ester or carboxylic ester groups. The ester group has strong polarity, and has stronger adhesion with the copper foil of the negative current collector and the negative active material. Therefore, the glass transition temperature of the binder is low, the whole polymer chain has stronger toughness, the material is soft, the elongation at break is high, and the mechanical property of the material is improved. When the material is used for a negative electrode of a secondary battery, under the condition of the same compaction density, the processing performance is excellent, so that the problem of battery performance caused by over brittleness of a pole piece is avoided. Meanwhile, the compaction density of the pole piece is improved, and the overall energy density of the battery is improved. On the other hand, the ester group has good affinity with the electrolyte and a certain swelling degree, is favorable for accelerating the transmission speed of ions at the interface of the active material and improving the dynamics of the negative electrode material, and is suitable for the use conditions of high-rate charge and discharge.
In addition, the binder is an anionic polymer, has strong dispersing and suspending capabilities on active substances, does not need to be additionally matched with sodium carboxymethyl cellulose, and can keep the use amount of the binder with a high proportion in the negative pole piece and enhance the binding performance. On the other hand, the process steps in the production process can be simplified, and the production efficiency is improved.
Therefore, in the binder of the present invention, one structural unit imparts self-healing property to the binder, and the other structural unit enhances the adhesive force of the binder, so that the secondary battery containing the binder has very excellent overall performance through the unique structural composition and the cooperation of the two structural units.
Therefore, the invention also relates to a secondary battery, which comprises a positive pole piece, a negative pole piece, a separation film and electrolyte, and is characterized in that at least one of the positive pole piece, the negative pole piece and the separation film contains the binder.
Preferably, the secondary battery contains the binder in a negative electrode tab.
For example, one method of preparing a negative electrode sheet using the binder of the present invention is as follows:
the binder, the conductive agent and the negative active material are mixed in deionized water to obtain slurry, and the obtained slurry is coated on a current collector to prepare a negative pole piece.
Therefore, in the secondary battery according to some embodiments of the present invention, the negative electrode sheet includes the binder, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material coating, and the negative electrode active material coating includes a conductive agent, a negative electrode active material, and the binder according to the present invention.
For example, another method for preparing a negative electrode sheet using the binder of the present invention is as follows:
the binder is directly coated on the current collector to form a current collector coating.
Therefore, in a secondary battery according to another embodiment of the present invention, a negative electrode sheet includes the binder, the negative electrode sheet includes a negative electrode current collector and a negative electrode active material coating, a coating is disposed between the negative electrode current collector and the negative electrode active material coating, and the coating includes the binder according to the present invention.
Any conventional conductive agent can be used in the above method, and the specific kind is not limited, and includes one or more of carbon nanotubes, conductive carbon black, carbon fibers and graphene.
Any conventional negative electrode active material can be used in the method, and the specific types are not limited, and may include one or more of hard carbon, soft carbon, mesocarbon microbeads, natural graphite, artificial graphite, surface-modified natural graphite, amorphous silicon, carbon-coated amorphous silicon particles, polycrystalline silicon particles, silicon monoxide particles, or silicon-based alloy powder.
Any conventional current collector may be used in the above method, and the specific kind is not limited, for example, various metal foils, preferably copper foil.
Preferably, in the secondary battery negative electrode plate, the binder accounts for 3-15% of the negative electrode active material layer formed by the binder, the conductive agent and the negative electrode active material by mass percent.
The secondary battery containing the binder of the present invention can have very excellent overall properties such as excellent cycle performance, high dynamic performance and high energy density.
Drawings
FIG. 1 is a diagram illustrating the self-healing effect of the adhesive block of the present invention;
fig. 2 is a graph comparing the adhesion of the negative electrode sheet prepared from the binder of example 1 of the present invention with the adhesion of the negative electrode sheets prepared from other binders (comparative examples 1 to 3).
Detailed Description
The invention will be further illustrated with reference to specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present application. In practice, the invention will be understood to be applicable to all modifications and variations of the invention as may be suggested to those skilled in the art.
First, examples 1 to 4
1. Preparation of the binder:
adding a certain amount of solvent (mixed solvent of N, N-dimethylformamide and water) into a four-neck flask provided with a condenser tube, a stirrer and a thermometer, introducing argon for 30min, and heating to 90 ℃; dropping a mixture of vinyl unsaturated amide sulfonic acid monomer (monomer unit shown in formula (I)), vinyl unsaturated ester monomer (monomer unit shown in formula (II) -1 or formula (II) -2) and azobisisobutyronitrile with a feeding amount at a constant speed under the protection of argon; after the dropwise addition, the reaction is carried out for a set time under the condition of heat preservation, and the solution is cooled to room temperature and then is spray-dried to obtain the solid powder of the binder.
By adjusting the molar contents of the two monomer units, 4 different binders were prepared, the specific reaction conditions, the monomer charge molar ratio, and the specific composition and number average molecular weight of the obtained binder are shown in tables 1-2, for example, in table 1-1.
Tables 1 to 1: binder preparation conditions of examples 1 to 4
Temperature/. degree.C Polymerization time/h The amount of the initiator is one percent by weight (I) And (II) the molar ratio of the feed
Example 1 80 24 0.7 10：1
Example 2 80 16 1.2 7.5：1
Example 3 80 8 2 5.2：1
Example 4 80 36 0.5 3：1
Tables 1 to 2: EXAMPLES 1-4 Binder compositions
Figure BDA0001520257950000101
*: the molar percentages of units of formula (I) and units of formula (II) in the binder were determined by elemental analysis (the same applies below).
2. Preparation of lithium ion secondary battery:
the binders of examples 1 to 4 prepared above were used to prepare corresponding lithium ion batteries. The lithium ion battery comprises a positive pole piece, a negative pole piece, an isolating membrane and electrolyte, and the material selection and preparation processes of all the components are briefly described as follows.
1) The positive pole piece comprises a positive current collector and a positive active material layer coated on the positive current collector. The positive current collector is an aluminum foil, and the positive active material layer comprises the following components in percentage by mass:
the positive electrode active material is LiNi1/3Mn1/3Co1/3O294.0 percent;
the positive electrode binder is polyvinylidene fluoride, and the content is 3.0%;
the positive electrode conductive agent is acetylene black with the content of 3.0 percent;
the positive current collector is aluminum foil with a thickness of 14 um.
2) The negative pole piece comprises a negative pole current collector and a negative pole active material layer coated on the negative pole current collector. The negative current collector is a copper foil, and the negative active material layer comprises the following components:
the negative active material is artificial graphite with the content of 95.0 percent;
the negative conductive agent is conductive carbon black with the content of 2.0 percent;
the negative electrode binders were the polymer materials prepared in examples 1 to 4, respectively, and the content was 3%;
the negative current collector is a copper foil with the thickness of 10 um.
3) The isolating membrane is a polyethylene porous film with the thickness of 14 um.
4) The electrolyte comprises an organic solvent and lithium salt, wherein the organic solvent is a mixture of diethyl carbonate, dimethyl carbonate and ethylene carbonate, and the volume ratio of the three solvents is 1: 1: 1, the lithium salt is LiPF6The concentration is 1 mol/L.
5) Preparing a lithium ion full battery:
preparing a positive pole piece: mixing 94.0% LiNi1/3Mn1/3Co1/3O2Adding 3.0% of polyvinylidene fluoride and 3.0% of acetylene black into an N-methylpyrrolidone (NMP) solvent system, fully stirring and uniformly mixing, coating on an aluminum foil, drying, and cold pressing to obtain the positive pole piece.
Preparing a negative pole piece: adding 95.0% of artificial graphite, 3.0% of binder and 2.0% of conductive carbon black into a deionized water solvent, fully stirring and uniformly mixing, coating on a copper foil, drying, and cold pressing to obtain the negative pole piece.
Preparing a battery: and stacking the positive pole piece, the isolating film and the negative pole piece in sequence to enable the isolating film to be positioned between the cathode and the anode to play an isolating role, and winding to obtain the bare cell. And (3) placing the naked battery core into an outer package, injecting the prepared electrolyte and packaging, and carrying out formation and aging on the battery core to obtain a corresponding lithium ion battery B1-B4.
Second, comparative examples 1 to 4
Lithium ion batteries of comparative examples 1 to 4 were prepared according to the method of example 1, except that the negative electrode binders used were different, and the compositions of the negative electrode binders of comparative examples 1 to 4 are specifically shown in table 2.
The manufacturing processes of the positive electrode piece, the negative electrode piece and the battery are the same as those of the embodiments 1 to 4, and the obtained batteries are CB1, CB2, CB3 and CB4 respectively.
Table 2: compositions of negative electrode binders of comparative examples 1 to 4
Figure BDA0001520257950000121
Third, comparative example 5 and example 5
The binders of comparative example 5 and example 5 were prepared according to the method of example 2, with the difference that: comparative example 5 in the binder preparation process, the reaction conditions such as the amount of the initiator and the polymerization time (specifically, see the following table 3-1) were adjusted to obtain a binder having a molecular weight of 15 ten thousand; example 5 in the preparation process of the binder, the reaction conditions such as the amount of the initiator and the polymerization time (see the following table 3-1) were adjusted to obtain a binder having a molecular weight of 164 ten thousand, and the specific composition of the binder is shown in the following table 3-2.
Table 3-1: binder preparation conditions for comparative example 5 and example 5
Temperature/. degree.C Polymerization time/h The amount of the initiator is one percent by weight (I) And (II) the molar ratio of the feed
Comparative example 5 80 24 2.5 7.5：1
Example 5 80 24 0.2 7.5：1
Tables 3-2: composition of negative electrode binders of comparative example 5 and example 5
Figure BDA0001520257950000131
The lithium ion batteries of comparative example 5 and example 5 were prepared according to the method of example 2, except that the binder was used, the manufacturing processes of the positive electrode tab, the negative electrode tab, the battery, and the like were kept unchanged, and the batteries obtained were CB5, B5, respectively.
Fourth, comparison of Performance test of examples 1-5 and comparative examples 1-5
(I) stress-strain test of adhesive film:
preparing the adhesive in the embodiments 1-5 into an aqueous solution with the mass fraction of 10%, filling a certain amount of the aqueous solution into a mold, and drying at 80 ℃ to obtain an adhesive film of the adhesive. Correspondingly, adhesive films in comparative examples 1 to 5 were prepared. And (3) taking the adhesive film with the same width and thickness, and testing a stress-strain curve to obtain the elastic modulus of the adhesive film before fracture. The adhesive film is manually cut from the middle, and then the adhesive film is butted to carry out self-repairing for a certain time (see attached figure 1), and the stress-strain curve is tested, so that the elastic modulus of the adhesive film after self-healing can be obtained.
Table 4: modulus of elasticity data of adhesive film (unit: MPa)
Modulus of elasticity before fracture Modulus of elasticity after self-healing
Example 1 388.6 352.7
Example 2 364.2 340.1
Example 3 355.4 335.7
Example 4 360.1 343.5
Example 5 345.1 320.9
Comparative example 1 53.5 0 (unable to self-heal)
Comparative example 2 27.6 0 (unable to self-heal)
Comparative example 3 90.6 0 (unable to self-heal)
Comparative example 4 170.4 63.8
Comparative example 5 150.6 57.1
From the above data, it can be seen that the adhesives prepared in examples 1-5 are self-healing aqueous adhesives having a modulus of elasticity after self-healing that is comparable to the modulus of elasticity before fracture. This shows that the aqueous binder of the present invention has very strong self-healing properties and good performance retention after healing, and when used in a lithium battery, the binder material can self-heal and substantially maintain its original performance even if the binder material structure is damaged due to various reasons, which has significant effects on improving the battery life and improving the battery performance. In contrast, the adhesives of comparative examples 1-3 do not have self-healing properties and do not repair themselves after structural damage; the adhesives of comparative examples 4 and 5 have a certain self-healing property, but the performance after self-healing is significantly reduced, so that the practicability is limited. The inventors believe that the self-healing properties of the binders of examples 1-5 are imparted by the first monomeric unit of structural formula (I), while the improved performance of examples 1-5 over comparative example 4 may be attributed to the introduction of the second monomeric unit comprising an alcohol ester group. Comparative example 5 performed poorly relative to examples 1-5, probably due to its too small molecular weight.
And (II) testing the adhesion of the negative pole piece:
before soaking the electrolyte: and cutting the coated and cold-pressed negative pole piece into a rectangle with the length of 100mm and the width of 10 mm. A stainless steel plate with the width of 25mm is taken, double-faced adhesive tapes (with the width of 11mm) are attached, the cut pole pieces are attached to the double-faced adhesive tapes on the stainless steel plate, and a 2000g compression roller is used for rolling the surface of the stainless steel plate back and forth for three times. And (3) bending the pole piece by 180 degrees, manually stripping the pole piece by 25mm, fixing the sample on a universal tensile machine, keeping the stripping surface consistent with the force line of a testing machine, continuously stripping the pole piece by the testing machine at 300mm/min to obtain a stripping force curve (shown in figure 2), and taking the average value of the stable sections as a stripping force F, wherein the bonding force of the tested negative pole piece is Fad which is F/0.01 (N/m).
After soaking the electrolyte: the negative pole piece after coating and cold pressing is cut into a rectangle with the length of 100mm and the width of 10mm, and the rectangle is soaked in electrolyte, wherein the electrolyte comprises an organic solvent and a lithium salt, the organic solvent is a mixture of diethyl carbonate, dimethyl carbonate and ethylene carbonate, and the volume ratio of the three solvents is 1: 1: 1, the lithium salt is LiPF61mol/L, and placing in a dry environment (relative humidity)<5%), soaking for 24h at room temperature, naturally volatilizing in a dry environment, and testing the pole piece bonding force after the solvent on the surface of the pole piece is completely volatilized. The test method and the adhesive force calculation method are the same as above. The test data are shown in table 5.
Table 5: cathode plate adhesion data (unit: N/m)
Before soaking in electrolyte After soaking in electrolyte
Example 1 83.2 40.7
Example 2 85.1 45.6
Example 3 80.7 42.5
Example 4 88.3 46.2
Example 5 80.3 42.3
Comparative example 1 18.3 9.4
Comparative example 2 12.6 5.7
Comparative example 3 46.3 20.8
Comparative example 4 61.4 31.4
Comparative example 5 15.4 10.7
From the comparison of the data above, it can be seen that: compared with the traditional binder, the self-healing water-based binder disclosed by the invention has remarkably stronger binding force to the pole piece, and the binding force is higher both before and after the electrolyte is soaked. This undoubtedly contributes to improving the performance of lithium batteries.
(III) testing the battery performance:
1. test of battery discharge rate performance
a. At normal temperature, the constant current charging is carried out to 4.25V at 0.5C, and the constant voltage charging is carried out to 0.05C, so that the charging is cut off. The constant current discharge of 0.2C is stopped to 3.0V, and the capacity is recorded, wherein the capacity is 100 percent;
b. at normal temperature, the constant current charging is carried out to 4.25V at 0.5C, and the constant voltage charging is carried out to 0.05C, so that the charging is cut off. Discharging at constant current of 0.5C to 3.0V, cutting off, recording the capacity, and calculating the percentage;
c. at normal temperature, the constant current charging is carried out to 4.25V at 0.5C, and the constant voltage charging is carried out to 0.05C, so that the charging is cut off. Discharging at constant current of 1.0C to 3.0V, cutting off, recording the capacity, and calculating the percentage;
d. at normal temperature, the constant current charging is carried out to 4.25V at 0.5C, and the constant voltage charging is carried out to 0.05C, so that the charging is cut off. Discharging at constant current of 2.0C to 3.0V, cutting off, recording the capacity, and calculating the percentage;
the test data are shown in Table 6.
Table 6: battery discharge rate capability
0.2C 0.5C 1.0C 2.0C
Example 1(B1) 100％ 98.5％ 96.7％ 93.0％
Example 2(B2) 100％ 98.3％ 95.4％ 93.1％
Example 3(B3) 100％ 97.5％ 94.3％ 92.5％
Example 4(B4) 100％ 97.0％ 94.0％ 92.6％
Example 5(B5) 100％ 90.1％ 86.2％ 82.5％
COMPARATIVE EXAMPLE 1(CB1) 100％ 92.1％ 87.1％ 82.5％
COMPARATIVE EXAMPLE 2(CB2) 100％ 90.0％ 85.3％ 77.3％
COMPARATIVE EXAMPLE 3(CB3) 100％ 94.5％ 90.1％ 88.6％
COMPARATIVE EXAMPLE 4(CB4) 100％ 95.3％ 93.7％ 90.2％
COMPARATIVE EXAMPLE 5(CB5) 100％ 85.6％ 80.4％ 75.3％
From the comparison of the data above, it can be seen that: the self-healing aqueous binder of the present invention significantly improves the discharge rate performance of lithium ion batteries over conventional binders, especially when the binder molecular weight is in the preferred range of 20-150 ten thousand.
2. Battery cycle life performance
a. At normal temperature, charging to 4.25V at a constant current of 0.5C, and stopping charging at a constant voltage of 0.05C;
b, discharging at constant current of 0.5C to 3.0V, stopping, and recording the capacity, wherein the capacity of the first battery is 100%;
c. and (5) repeating the steps 1-2, and recording the percentage of the residual capacity of the battery.
The test data are shown in Table 7.
Table 7: battery cycle life performance
Initial 100 cycles 200 cycles 300 cycles
Example 1(B1) 100％ 98.4％ 96.7％ 94.4％
Example 2(B2) 100％ 96.2％ 95.3％ 94.0％
Example 3(B3) 100％ 94.3％ 92.6％ 90.8％
Example 4(B4) 100％ 95.7％ 93.9％ 91.4％
Example 5(B5) 100％ 91.3％ 89.4％ 87.1％
COMPARATIVE EXAMPLE 1(CB1) 100％ 90.3％ 87.5％ 84.3％
COMPARATIVE EXAMPLE 2(CB2) 100％ 89.1％ 85.4％ 82.6％
COMPARATIVE EXAMPLE 3(CB3) 100％ 91.1％ 88.3％ 86.2％
COMPARATIVE EXAMPLE 4(CB4) 100％ 90.5％ 88.6％ 85.9％
COMPARATIVE EXAMPLE 5(CB5) 100％ 89.3％ 87.4％ 84.5％
From the comparison of the data above, it can be seen that: compared with the traditional binder, the self-healing water-based binder provided by the invention has the advantage that the cycle life of the lithium ion battery is obviously prolonged.
Fifth, examples 6 to 9
A binder was prepared as in example 1, and the polymer had a structure comprising a monomer unit of formula (I) as a first component and a monomer unit of formula (II) -1 as a second component, wherein the formula and the composition of the two monomer units are shown in Table 8.
Table 8: binder compositions of examples 6-9
Figure BDA0001520257950000171
The adhesives of the structural formulas of the examples 6-9 are prepared according to the method of the example 1, the adhesives of the examples 6-9 also have excellent self-healing property and obviously better adhesive force to a pole piece than the comparative example through testing, and the performance of the prepared lithium ion battery is similar to that of the lithium ion battery of the examples 1-4.
Sixth, examples 10 to 13
A binder was prepared as in example 1, and the polymer had a structure comprising a monomer unit of formula (I) as a first component and a monomer unit of formula (II) -2 as a second component, wherein the formula and the composition of the two monomer units are shown in Table 9.
Table 9: binder compositions of examples 10-13
Figure BDA0001520257950000181
The adhesives of the structural formulas of the examples 10-13 are prepared according to the method of the example 1, the adhesives of the examples 10-13 also have excellent self-healing property and obviously better adhesive force to a pole piece than the comparative example through testing, and the performance of the prepared lithium ion battery is similar to that of the lithium ion batteries of the examples 1-4.
Although the present application has been described with respect to the preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the present application.

Claims (10)

1. An aqueous binder which is a polymer comprising at least two kinds of monomer units, wherein one of the monomer units is a unit represented by the formula (I) containing both a sulfonic acid group and an amide group, and the other monomer unit is a unit represented by the formula (II) -1,
Figure FDA0002504378560000011
wherein, in the structural formula (I), R1Selected from H, C1-6 linear or branched alkylnH2nIs a straight-chain or branched alkylene group with n being 1-8, and X is selected from hydrogen ions, lithium ions, sodium ions, potassium ions, rubidium ions, cesium ions or ammonium ions;
in the structural formula (II) -1, R1Selected from H, C1-6 straight chain or branched chain alkyl, R2Selected from H, benzoyl, straight chain or branched chain alkanoyl with total carbon atoms of 1-8;
r in the formula (I)1With R in the formula (II) -11Are each independently selected;
the structural unit shown in the structural formula (I) accounts for 40-90% of the molar percentage of the binder, and the structural unit shown in the structural formula (II) -1 accounts for 10-60% of the molar percentage of the binder; and is
The number average molecular weight of the binder is 20-150 ten thousand.
2. Binder according to claim 1, wherein the units of formula (I) are selected from the group consisting of poly (sodium 2-acrylamido-2-methylpropanesulfonate) segments, poly (3-methacrylamido-2-methyl-1-propanesulfonic acid) segments, poly (lithium 3-acrylamido-2, 2-dimethyl-1-propanesulfonate) segments, poly (ammonium 3-acrylamido-1-propanesulfonate) segments, poly (potassium 3-methacrylamido-2, 3-dimethyl-2-butanesulfonate) segments.
3. The binder according to claim 1, wherein the unit of formula (II) -1 is selected from: a polyvinyl alcohol segment, a polyvinyl acetate segment, a polyvinyl benzoate segment, a polyvinyl propionate segment, or a polyvinyl n-butyrate segment.
4. The binder of claim 1 wherein the mole percentage of structural units of formula (I) in the binder is 50 to 80%.
5. The binder of claim 1, wherein the structural unit of formula (II) -1 is present in a molar percentage of 20 to 50% of the binder.
6. A binder as claimed in any one of claims 1 to 5, characterized in that the number average molecular weight of the binder is between 40 and 110 ten thousand.
7. The binder as claimed in any one of claims 1 to 5, wherein the binder is composed of units of formula (I) and units of formula (II) -1.
8. A secondary battery comprising a positive electrode sheet, a negative electrode sheet, a separator and an electrolyte, wherein at least one of the positive electrode sheet, the negative electrode sheet and the separator contains the binder according to any one of claims 1 to 7.
9. The secondary battery according to claim 8, which is a lithium ion battery, the negative electrode tab comprises a negative electrode current collector and a negative electrode active material coating, the negative electrode active material coating comprises a conductive agent, a negative electrode active material and the binder according to any one of claims 1 to 7.
10. The secondary battery according to claim 8, which is a lithium ion battery, the negative electrode sheet comprises a negative electrode current collector and a negative electrode active material coating, a coating is arranged between the negative electrode current collector and the negative electrode active material coating, and the coating comprises the binder according to any one of claims 1 to 7.
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