CN107710470A - Negative pole adhesive, negative electrode slurry composition and the negative pole and lithium rechargeable battery of lithium rechargeable battery - Google Patents
Negative pole adhesive, negative electrode slurry composition and the negative pole and lithium rechargeable battery of lithium rechargeable battery Download PDFInfo
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- CN107710470A CN107710470A CN201680034156.9A CN201680034156A CN107710470A CN 107710470 A CN107710470 A CN 107710470A CN 201680034156 A CN201680034156 A CN 201680034156A CN 107710470 A CN107710470 A CN 107710470A
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- Prior art keywords
- monomer
- negative pole
- adhesive
- compound
- carboxylic
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
- C08F290/126—Polymers of unsaturated carboxylic acids or derivatives thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The problem of the present invention is, there is provided a kind of negative pole adhesive of the excellent material as lithium rechargeable battery of speed characteristic.The present invention provides a kind of adhesive, and it is the lithium ion secondary battery negative pole adhesive containing the dispersion liquid that nuclear cap type high molecular particle is dispersed with aqueous dispersion medium, wherein, the nuclear cap type high molecular particle has following structure：The hydrophily bizet formed by the construction unit from the micro- monomer of carboxylic hydrophily is surrounded around the hydrophobic core portion formed by the construction unit from hydrophobic monomer.
Description
Technical field
The present invention relates to negative pole adhesive, negative electrode slurry composition and the negative pole of a kind of lithium rechargeable battery and
Lithium rechargeable battery.
Background technology
Lithium rechargeable battery due to for light weight and energy density it is high, it is high relative to the durability for repeating discharge and recharge, therefore,
Power supply as electronic devices such as mobile phone, notebook computers is used.In addition, in the electric cars such as electric automobile, also serving as can
It is used effectively with the supply unit for being discharged and being charged.
Lithium rechargeable battery generally has following structure：By the two sides of positive electrode collector formed with containing positive electrode active material
The positive pole of the positive electrode active material layer of matter and the two sides of negative electrode collector are formed with the negative electrode active material containing negative electrode active material
The negative pole of matter layer connects via dielectric substrate, and is stored in battery case.
The negative pole of lithium rechargeable battery is the powdered graphite by being used as negative electrode active material in the coating of collector surface
With the mixed slurry of negative pole adhesive and be dried and formed.Negative pole has by the use of adhesive will be as negative electrode active material
Graphite composite powder bonded each other, while the work that will be bonded as the metal foils such as the copper foil of collector and graphite composite powder
With.Negative pole with this effect is worked by the use of adhesive in negative pole as internal resistance, it is therefore desirable to for can be with a small amount of
Show the material of high cohesive force.And then because the species of adhesive has an impact to the output characteristics (speed characteristic) of battery, because
This, it is desirable to the good negative pole adhesive of speed characteristic.
As the resin of the main component as negative pole adhesive, at present, Kynoar is used in the same manner as positive pole
(PVDF).PVDF is because cohesive force is insufficient, therefore, recently using styrene-butadiene latex (SBR) etc. (such as patent text
Offer 1 and 2).But the negative pole containing SBR is with adhesive that its speed characteristic is insufficient.
Because the requirement of the raising of the speed characteristic to lithium rechargeable battery increasingly increases, therefore, it is desirable to speed characteristic
Excellent negative pole adhesive.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 04-051459 publications
Patent document 2：Japanese Unexamined Patent Publication 05-074461 publications
The content of the invention
Invent problem to be solved
In this condition, to solve the present invention major subjects be, there is provided a kind of speed characteristic it is excellent turn into lithium from
The negative pole adhesive of the material of sub- secondary cell.
For solving the technical scheme of problem
The present inventor in order to develop the negative pole adhesive of the excellent material as lithium rechargeable battery of speed characteristic,
Further investigation is repeated, as a result finds：Made by regarding the dispersion liquid for containing core-crown type high molecular particle as adhesive
With can solve above-mentioned problem, wherein the core-crown type high molecular particle has following structure：By from carboxylic hydrophilic
Property micro- monomer the hydrophily bizet that is formed of construction unit surround the hydrophobicity that is formed by the construction unit from hydrophobic monomer
Around core portion.Based on such opinion, research is further repeated, as a result completes the present invention.
That is, the present invention relates to the lithium ion secondary battery negative pole adhesive shown in following items 1~6, lithium ion secondary electricity
Pond negative electrode slurry composition, lithium ion secondary battery negative pole and lithium rechargeable battery.
A kind of 1. adhesives of item, it is the lithium containing the dispersion liquid that core-crown type high molecular particle is dispersed with aqueous dispersion medium
Ion secondary battery negative pole adhesive, wherein,
The core-crown type high molecular particle has following structure：By the construction unit shape from the micro- monomer of carboxylic hydrophily
Into hydrophily bizet surround around the hydrophobic core portion formed by the construction unit from hydrophobic monomer.
2. adhesives described in item 1 as described above, wherein, the core-crown type high molecular particle is described carboxylic hydrophilic to make
Property micro- monomer and the hydrophobic monomer carry out the high molecular particle that forms of radical polymerization,
The micro- monomer of carboxylic hydrophily is carboxylic high-molecular compound and intramolecular is had polymerism reactive group
Group and with carboxyl reaction and form micro- monomer for forming of compound reaction of both functional groups of covalent bond.
3. intramoleculars have polymerism reactive group and with carboxyl reaction and form both functional groups of covalent bond
Compound is to be represented selected from compound, the compound of following formulas (2) expression and the formula (3) represented by following formulas (1)
At least one kind of compound in the group that compound is formed,
【Chemical formula 1】
[in formula, R1Represent hydrogen atom or methyl.Q1Represent oxygen atom or-NH-.]
【Chemical formula 2】
[in formula, R2Represent hydrogen atom or methyl.Q2Represent oxygen atom or-NH-.N represents 1~4 integer.]
【Chemical formula 3】
[in formula, R3Represent hydrogen atom or methyl.R4Represent hydrogen atom, the alkyl or halogen atom of carbon number 1~4.X1Table
Show halogen atom.].
A kind of 4. lithium ion secondary battery negative pole paste compounds, its contain lithium any one of above-mentioned item 1~3 from
Sub- secondary battery negative pole adhesive and active material.
A kind of 5. lithium ion secondary battery negative poles of item, it is to be coated with the lithium rechargeable battery described in above-mentioned item 4 on the current collector
Negative electrode slurry composition is simultaneously dried and formed.
A kind of 6. lithium rechargeable batteries of item, it contains the lithium ion secondary battery negative pole described in above-mentioned item 5.
Invention effect
The lithium ion secondary battery negative pole adhesive of the present invention passes through the core containing particulate form-crown type macromolecule chemical combination
Thing, spot gluing can be carried out on negative electrode active material surface and collector surface, without prejudice to contacting between negative electrode active material, born
Contact between pole active material and collector and make to bond between negative electrode active material and negative electrode active material and current collection
Bonded between body, meanwhile, it can also be improved between negative electrode active material using the hydrophily bizet for being present in high molecular particle surface
And the caking property of negative electrode active material and collector, therefore, it is possible to reduce electrode resistance.And then hydrophobic core can be followed
The swelling of negative electrode active material during portion's discharge and recharge shrink caused by Volume Changes, thereby, it is possible to prevent between negative electrode active material
And the contact portion of negative electrode active material and collector lose and produce do not obtain conducting part (negative electrode active material it is electric
Isolation).Therefore, by using this lithium ion secondary battery negative pole adhesive, the excellent lithium of speed characteristic can be obtained
Ion secondary battery.
Brief description of the drawings
Fig. 1 is the skeleton diagram for the mechanism for obtaining core-crown type high molecular particle.
Fig. 2 is the curve map of the speed characteristic for the evaluation half-cell for representing embodiment 1,4 and 5 and comparative example 1.
Fig. 3 is the curve map of the impedance measuring result for the evaluation half-cell for representing embodiment 1 and comparative example 1.
Embodiment
Hereinafter, the lithium ion secondary battery negative pole adhesive to the present invention, lithium ion secondary battery negative pole slurry group
Compound, lithium ion secondary battery negative pole and lithium rechargeable battery specifically illustrate.
1. lithium ion secondary battery negative pole adhesive
The lithium ion secondary battery negative pole of the present invention is situated between with adhesive (following, sometimes referred to simply as " adhesive ") containing aqueous dispersion
The dispersion liquid of core-crown type high molecular particle is dispersed with matter.
The key character of the adhesive of the present invention is that the core-crown type high-molecular compound being scattered in dispersion liquid is formed
Particulate form, core-crown type high molecular particle have following structure：By the construction unit shape from the micro- monomer of carboxylic hydrophily
Into hydrophily bizet surround around the hydrophobic core portion formed by the construction unit from hydrophobic monomer.
Particulate form is formed by core-crown type high-molecular compound, can be in negative electrode active material surface and current collection body surface
Face carries out spot gluing, makes to bear without prejudice to the contact between the contact between negative electrode active material, negative electrode active material and collector
Pole active material bonds between bonding and negative electrode active material and collector each other, it is thereby possible to reduce electrode resistance.This
Be because the hydrophily bizet for being present in the surface of high molecular particle has many carboxyls, the carboxyl and negative electrode active material
Compatibility is excellent, and therefore, adhesive of the invention is homogeneously dispersed in negative electrode active material layer, can improve negative electrode active material
Between matter and the caking property of negative electrode active material and collector.In addition, by hydrophobic core portion by forming glass transition temperature
(Tg) hydrophobic monomer of low high-molecular compound is formed, and the swelling of negative electrode active material when can follow discharge and recharge is received
Volume Changes caused by contracting, thus it can be prevented that between negative electrode active material and the funeral of the contact portion of negative electrode active material and collector
Lose and produce the part (the electric isolation of negative electrode active material) for not obtaining conducting.Electricity is formed by using this adhesive
Pole, the stripping of negative electrode active material caused by charge and discharge cycles tail off, therefore, by using the lithium rechargeable battery of the present invention
Negative pole adhesive, the excellent lithium rechargeable battery of speed characteristic can be obtained.
Above-mentioned core-crown type high molecular particle is the micro- monomer of carboxylic hydrophily and hydrophobic monomer is carried out radical polymerization
Close the high molecular particle formed.
Hereinafter, the above-mentioned carboxylic micro- monomer of hydrophily is illustrated.
The above-mentioned micro- monomer of carboxylic hydrophily is by making carboxylic high-molecular compound and intramolecular have polymerization
Property reactive group and with carboxyl reaction and formed both functional groups of covalent bond compound reaction obtained from.
As long as above-mentioned carboxylic high-molecular compound change containing carboxyl in the repeat unit of high-molecular compound
Compound, just it is not particularly limited, the polymer such as carboxylic monomer can be enumerated, carboxylic polysaccharide.
As above-mentioned carboxylic monomer, it can enumerate and contain carbon-to-carbon unsaturated double-bond and carboxyl and/or its salt as necessary
The monomer of composition.As this monomer, can enumerate for example：(methyl) acrylic acid, butenoic acid, Alpha-hydroxy acrylic acid, Alpha-hydroxy first
The unsaturated monocarboxylics such as base acrylic acid and their salt；The unsaturations such as itaconic acid, fumaric acid, maleic acid, 2- methyleneglutaric acids
Dicarboxylic acids and their salt etc..These monomers can be used alone, or be mixed with two or more.It is explained, this explanation
In book, " (methyl) acrylic acid " is the meaning of acrylic acid and/or methacrylic acid.
As above-mentioned carboxylic polysaccharide, can enumerate for example：The carboxyalkyls such as carboxymethyl cellulose, carboxy ethyl cellulose
Cellulose；CMS, carboxy methyl amylose, hyaluronic acid, alginic acid, pectin and their salt etc..These polysaccharide can
To be used alone a kind, or it is mixed with two or more.
As above-mentioned salt, metal salt, ammonium salt, organic amine salt etc. can be enumerated.As metal salt, can enumerate for example：Lithium salts, sodium
The alkali metal salts such as salt, sylvite；The alkali salts such as magnesium salts, calcium salt；Aluminium salt, molysite etc..As organic amine salt, can enumerate for example：
The alkanol amine salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt；MEA salt, diethyl amine salt, triethyl amine salt
Deng alkylamine salt；Polyamine such as ethylenediamine salt, triethylenediamine etc..Their salt can be used alone, or be used in mixed way 2 kinds with
On.
As the polymer of above-mentioned carboxylic monomer raw material monomer in addition to above-mentioned carboxylic monomer, can group
Close can with the non-ionic monomer of the monomer copolymerization and use.As this non-ionic monomer, can enumerate for example：Acryloyl
Amine, Methacrylamide, positive N-isopropylacrylamide, methyl acrylate, methyl methacrylate etc..
The homopolymer or copolymer of carboxylic monomer or combination have the copolymerization of carboxylic monomer and non-ionic monomer
Thing can be manufactured by known polymerization.Above-mentioned carboxylic high-molecular compound can be used alone, or
It is mixed with two or more.As above-mentioned carboxylic high-molecular compound, preferably polyacrylic acid and its salt, more preferably polypropylene
Sour sodium.
As the ratio of the carboxylic construction unit in above-mentioned carboxylic high-molecular compound, preferably producing high-molecular
60 moles of more than % of the full construction unit of compound, more preferably 80 moles of more than %, particularly preferably full construction unit is containing carboxyl
Construction unit.
As long as the number that the molecular weight of above-mentioned carboxylic high-molecular compound is obtained by known manufacture method is divided equally
Son amount, is just not particularly limited, preferably 500~500,000 or so.
There is polymerism reactive group as above-mentioned intramolecular and formed with carboxyl reaction covalent bond functional group this two
The compound (following, sometimes referred to as " compound containing functional group ") of person, can be enumerated for example：The chemical combination that following formulas (1) represent
Thing (hereinafter also referred to as " compound (1) "), following formulas (2) represent compound (hereinafter also referred to as " compound (2) ") and
Compound (hereinafter also referred to as " compound (3) ") that formula (3) represents etc..
【Chemical formula 4】
[in formula, R1Represent hydrogen atom or methyl.Q1Represent oxygen atom or-NH-.]
【Chemical formula 5】
[in formula, R2Represent hydrogen atom or methyl.Q2Represent oxygen atom or-NH-.N represents 1~4 integer.]
【Chemical formula 6】
[in formula, R3Represent hydrogen atom or methyl.R4Represent hydrogen atom, the alkyl or halogen atom of carbon number 1~4.X1Table
Show halogen atom.]
As the above-mentioned compound containing functional group, can use select free compound (1), compound (2) and compound (3)
At least one kind of compound in the group of composition.
In above-mentioned formula (1), R1Represent hydrogen atom or methyl, Q1Represent oxygen atom or-NH-.
As above-claimed cpd (1), can enumerate for example：Glycidyl acrylate, GMA, contracting
The vinyl monomers containing glycidyl such as water glyceryl acrylamide, glycidol butylmethacrylamide.These chemical combination
Thing can be used alone, or be mixed with two or more.
In above-mentioned formula (2), R2Represent hydrogen atom or methyl.Q2Represent oxygen atom or-NH-.N is 1~4 integer, preferably
For 2.
As above-claimed cpd (2), can enumerate for example：Isocyanate ethyl acrylate, isocyanate ethyl methyl-prop
The vinyl containing NCO such as olefin(e) acid ester, isocyanate ethyl acrylamide, isocyanate ethyl Methacrylamide
It is monomer.These compounds can be used alone, or be mixed with two or more.
In above-mentioned formula (3), R3Represent hydrogen atom or methyl.R4Represent that hydrogen atom, the alkyl of carbon number 1~4 or halogen are former
Son.X1Represent halogen atom.
As R4The alkyl of shown carbon number 1~4, can be enumerated：Methyl, ethyl, n-propyl, isopropyl, normal-butyl
Deng as halogen atom, can enumerating：Fluorine atom, chlorine atom, bromine atoms, iodine atom etc..
As X1Shown halogen atom, it can enumerate：Fluorine atom, chlorine atom, bromine atoms, iodine atom etc..
In above-mentioned formula (3), R3Preferably hydrogen atom, R4Preferably hydrogen atom, X1Preferably chlorine atom or bromine atoms.
As above-claimed cpd (3), can enumerate for example：1-chloro-4-methyl-benzene, bromometllylstyrene, iodomethyl styrene
Deng.These compounds can be used alone, or be mixed with two or more.
Above-mentioned carboxylic high-molecular compound and the above-mentioned compound containing functional group is set to react the carboxylic parent formed
The synthesis of water-based micro- monomer can be by making above-mentioned carboxylic high-molecular compound and above-mentioned containing functional group in an aqueous medium
Compound usual 10~80 DEG C or so, preferably 20~60 DEG C or so reaction and carry out.
As aqueous medium, can use：Water；The alcohol such as methanol, ethanol, propyl alcohol；The ketone such as acetone, MEK；Dimethyl methyl
Acid amides etc..As aqueous medium, water can be used alone, using mixed solvent of the mixed solvent of alcohol and water, ketone and water etc., it is excellent
Water is used alone in choosing.
The ratio of above-mentioned carboxylic high-molecular compound and the above-mentioned compound containing functional group is not particularly limited, preferably
Relative to 100 moles of the carboxylic construction unit of above-mentioned high-molecular compound, using upper in the range of 40~1 moles or so
State the compound containing functional group.The more preferably scope of the above-mentioned compound containing functional group is 35~1 moles or so, particularly preferred
Scope is 10~1 moles or so.
Here, it is any of compound (1), compound (2) or compound (3) in the above-mentioned compound containing functional group
In the case of, the ratio of the above-mentioned compound containing functional group is the single ratio of the compound.In the above-mentioned compound containing functional group
Inclusion compound (1), compound (2) or compound (3) it is of more than two kinds in the case of, make the ratio of total contained total compound
Rate turns into above range.
The reaction of above-mentioned carboxylic high-molecular compound and above-claimed cpd (1) is carboxyl relative to glycidyl
Necleophilic reaction.The reaction of above-mentioned carboxylic high-molecular compound and above-claimed cpd (2) is carboxyl relative to NCO
Necleophilic reaction.Parent of the reaction of above-mentioned carboxylic high-molecular compound and above-claimed cpd (3) for carboxyl relative to benzyl
Nuclear reaction.
Reaction time is different because of reaction temperature etc., usually 30 minutes~10 hours or so.
In the synthesis of the micro- monomer of carboxylic hydrophily, preferably using polyacrylic acid or polyacrylate as containing carboxyl
High-molecular compound, as at least 1 in the group being made up of above-claimed cpd (1), compound (2) and compound (3)
Kind compound, preferably using compound (1).In compound (1), more preferably using GMA.
Therefore, as the above-mentioned carboxylic micro- monomer of hydrophily, preferably by as above-mentioned carboxylic high-molecular compound
Polyacrylic acid or polyacrylate and the above-claimed cpd (1) as the above-mentioned compound containing functional group be methacrylic acid contracting
Micro- monomer that the combination of water glyceride obtains.For example, when being polyacrylate as above-mentioned carboxylic high-molecular compound
One of the structure of micro- monomer, the structure of following formula (4a) expression can be enumerated,
【Chemical formula 7】
(in formula, M represents alkali metal ion, ammonium ion or organoammonium ions, and l and m are the whole of expression number of repeat unit
Number).In said structure, M be sodium ion in the case of, preferably following formula (4b) represent structure,
【Chemical formula 8】
(in formula, l and m are same as described above).
By the micro- monomer of carboxylic hydrophily and hydrophobic monomer that make so to obtain in the presence of polymerization initiator,
It is copolymerized in an aqueous medium, core-crown type high molecular particle can be obtained.
As above-mentioned hydrophobic monomer, the known hydrophobicity list with ethylenic unsaturated bond group can be widely used
Body, it can enumerate for example：Styrenic monomers, (methyl) acrylate, vinyl monomer, hydrocarbon conjugated diene monomer etc..Make
For above-mentioned styrenic monomers, can enumerate：Styrene, methyl styrene, dimethyl styrene, chlorostyrene, dichlorostyrene,
1-chloro-4-methyl-benzene, 4- methoxy styrenes, 4- acetoxy-styrenes etc..As above-mentioned (methyl) acrylate, can enumerate：
(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (first
Base) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) 2-EHA, (methyl) cyclohexyl acrylate,
(methyl) acrylic acid n-dodecane base ester, (methyl) stearyl acrylate ester, (methyl) phenyl acrylate, (methyl) acrylic acid benzyl
Ester, (methyl) acrylic acid 2- hydroxy methacrylates etc..As above-mentioned vinyl monomer, can enumerate：Vinylacetate, vinyl propionate
Ester, vinyl benzoate, N- butylacrylamides, acrylonitrile, vinyl chloride etc..As above-mentioned hydrocarbon conjugated diene monomer, can lift
Go out：1,3- butadiene, isoprene, 2,3- dimethyl -1,3- butadiene, 1,3- pentadienes, 1,3- hexadienes, 1,3- heptan two
Alkene, 2- phenyl -1,3- butadiene, 3- methyl-1,3-pentylenes etc..These monomers can be used alone, or be used in mixed way 2
More than kind.In above-mentioned monomer, from the viewpoint of the glass transition temperature of obtained high-molecular compound, preferably (methyl)
Acrylate, more preferably (methyl) 2-EHA.
Cross-linked structure can also be imported in the hydrophobic core portion of high molecular particle.Therefore, it is possible to use divinylbenzene, second
The hydrophobic monomer of the function of diol dimethacrylate etc. 2.The hydrophobic monomer of 2 functions is micro- preferably with respect to macromolecule is formed
Whole free radical polymerization monomers of the core of grain, are used, more preferably 0.1~10 weight in the range of 0.01~20 weight % or so
Measure % or so.
As aqueous medium, can use：Water；The alcohol such as methanol, ethanol, propyl alcohol；The ketone such as acetone, MEK；Dimethyl methyl
Acid amides etc..As aqueous medium, water can be used alone, using mixed solvent of the mixed solvent of alcohol and water, ketone and water etc., it is excellent
Water is used alone in choosing.It is explained, conjunction of the aqueous medium as used herein preferably with the above-mentioned micro- monomer of carboxylic hydrophily
It is identical into the middle aqueous medium used.
As polymerization initiator, known polymerization initiator can be widely used, can be enumerated for example：Ammonium persulfate, over cure
Double (propane of the 2- amino two) salt of sour potassium, hydrogen peroxide, benzoyl peroxide, TBHP, azobis isobutyronitrile, azo
Hydrochlorate etc..Polymerization initiator can be used alone, or be mixed with two or more.Polymerization initiator is preferably with respect to hydrophobicity
100 moles of monomer, uses 0.1~10 mole or so.Known molecular weight regulator can also be added as needed on.
As polymerization temperature, preferably 50~100 DEG C.
Polymerization time changes according to the species and usage amount of polymerization initiator, polymerization temperature etc., usually 30 points
Clock~10 hour or so.Hydrophobic monomer that the core portion of particulate is formed and the micro- monomer of hydrophily is contributed to preferably to enter by polymerization
Row polymerization is to being consumed.
In the synthesis of high molecular particle, the ratio of the micro- monomer of hydrophily and hydrophobic monomer is not particularly limited.It is hydrophilic
The property repeat unit of micro- monomer and the ratio of hydrophobic monomer are preferably 1：100~0.01 scope, more preferably 1：10~0.05
Scope, particularly preferred 1：5~0.1 scope.
Hereinafter, reference picture 1, illustrate to obtain the mechanism of core-crown type high molecular particle.Fig. 1 schematically represents to obtain containing carboxylic
The typical mechanism of high molecular particle when the micro- monomer of hydrophily and hydrophobic monomer of base are copolymerized.Carboxylic hydrophily
Micro- monomer 1 is made up of acrylic acid units 1a and the side chain 1b containing vinyl.First, by the micro- He of monomer 1 of carboxylic hydrophily
Hydrophobic monomer 2 is mixed (process A), when being polymerize hydrophobic monomer, partly causes the polymerization of hydrophobic monomer
(process B), simultaneously, cause and the copolymerization of the side chain 1b containing vinyl.The result of copolymerization, it can obtain having just like thin
The high-molecular compound of structure as the micro- monomer of carboxylic hydrophily has been carried out grafting by the polymer of aqueous monomers.By
Carried out in an aqueous medium in reaction, therefore, be accumulated in inner side the polymeric oxidizer of hydrophobic monomer, it is carboxylic hydrophilic
Property micro- monomer 1 be optionally accumulated in outside (process C).At the end of so polymerizeing, it can obtain by from carboxylic hydrophily
The hydrophily bizet 4 that the construction unit of micro- monomer is formed is located at the hydrophobic core formed by the construction unit from hydrophobic monomer
The high molecular particle 5 (step D) on the surface in portion 3.
The present invention lithium ion secondary battery negative pole with adhesive contain it is above-mentioned be dispersed with aqueous dispersion medium core-
The dispersion liquid of crown type high molecular particle.
As aqueous dispersion medium, can use：Water；The alcohol such as methanol, ethanol, propyl alcohol；The ketone such as acetone, MEK；Diformazan
Base formamide etc..As aqueous dispersion medium, water, the mixing using the mixed solvent of alcohol and water, ketone and water can be used alone
Solvent etc., is preferably used alone water.
The amount of the lithium ion secondary battery negative pole of the present invention by the use of high molecular particle contained in adhesive is used as the dispersion liquid
Solid constituent amount, usually 10~60 weight %, preferably 15~50 weight %.
The presence of high molecular particle is such as can utilize transmission electron microscope method, optical microscopy and easily
Confirm.The volume average particle size of high molecular particle is 1nm~1000nm, preferably 10nm~500nm.Volume average particle size can be with
It is measured using such as Zetasizer, Microtrac.
The method for obtaining above-mentioned dispersion liquid is not particularly limited.Excellent etc. from manufacture efficiency considers, preferably uses
Such as：High molecular particle is manufactured by method as described above and is scattered in the latex that aqueous medium forms, obtained latex is straight
Connect the method as dispersion liquid；Method that the aqueous medium of obtained latex is replaced with into other aqueous mediums etc..As scattered
The replacement method of medium, it can enumerate and high molecular particle is for example manufactured in alcohol, the alcohol be replaced with water-based beyond above-mentioned alcohol
During medium, added in latex after the aqueous medium beyond alcohol, using the way of distillation, filtration method, decentralized medium are mutually changed respectively
Method etc. removes method of alcohol composition in decentralized medium etc..
Obtained dispersion liquid can be used directly as negative pole with adhesive.Or in addition to dispersion liquid, can suitably it add
Add the additives such as the viscosity modifier for improving coating, flowing agent and use.As these additives, can enumerate：Carboxylic first
The cellulosic cpds such as base cellulose, methylcellulose, hydroxy propyl cellulose；And these ammonium salts and alkali metal salt；Poly- (first
Base) polyacrylate such as PAA；Polyvinyl alcohol, PEO, PVP, (methyl) acrylic acid or
The copolymer of (methyl) acrylates and vinyl alcohol, maleic anhydride or maleic acid or the copolymer of fumaric acid and vinyl alcohol, modification
Polyvinyl alcohol, modified poly- (methyl) acrylic acid, polyethylene glycol, polycarboxylic acids, ethylene-vinyl alcohol copolymer, Polymerization of Vac
Water-soluble polymers such as thing etc..The use ratio of these additives can be selected suitably as needed.
And then adhesive of the invention can contain the polymer or polymer particle beyond above-mentioned high molecular particle.
In general these polymer or polymer particle can widely use known polymer as battery electrode adhesive.Its
Usage amount is below 1 parts by weight preferably with respect to the above-mentioned parts by weight of high molecular particle 1.
The adhesive of the present invention is the dispersion liquid for including the core manufactured with method as described above-crown type high molecular particle.
The PVDF of the solvent soluble type used currently as adhesive resin, in order to be matched somebody with somebody in a manner of applying negative electrode active material surface
To put and hinder the contact between contact and negative electrode active material and the collector between negative electrode active material, electrode resistance becomes big, with
This is relative, and core-crown type high-molecular compound of particulate form is contained by the adhesive of the present invention, can be in negative electrode active material
Surface and collector surface carry out spot gluing, without prejudice to the contact between negative electrode active material, negative electrode active material and collector it
Between contact and make to bond between negative electrode active material and negative electrode active material and collector between bond, therefore, can be with
Reduce electrode resistance.
And then core-crown type high molecular particle is different from the SBR used currently as adhesive resin, due in high score
There is the hydrophily bizet high with negative electrode active material and collector compatibility in sub- microparticle surfaces, therefore, in the discharge and recharge repeated
Also the caking property and negative electrode active material between negative electrode active material are kept in the dilation of caused negative electrode active material
Caking property between matter and collector, can be by maintaining contact, negative electrode active material and collector between negative electrode active material
Between contact portion and holding electrode resistance smaller.
In addition, negative electrode active material when the hydrophobic core portion of core-crown type high molecular particle can follow discharge and recharge
Volume Changes caused by swelling contraction, therefore, in the dilation of the negative electrode active material of occlusion and releasing with lithium ion
During, it can prevent between negative electrode active material and the contact portion of negative electrode active material collector is lost and produces not obtain and leads
Logical part (the electric isolation of negative electrode active material).
Therefore, by using this lithium ion secondary battery negative pole adhesive, the excellent lithium of speed characteristic can be obtained
Ion secondary battery.
2. lithium ion secondary battery negative pole paste compound
The lithium ion secondary battery negative pole paste compound of the present invention contains above-mentioned adhesive and active material of the invention.
The lithium ion secondary battery negative pole paste compound of the present invention can be by by above-mentioned adhesive and active matter of the invention
Matter is mixed and prepared.
As long as the material that active material uses in the manufacture of common electrode for lithium ion secondary battery, then any
It can use.As negative electrode active material, can enumerate：The graphite such as native graphite, Delanium, expanded graphite system carbon material
The carbonaceous material such as (graphite), carbon black, activated carbon, carbon fiber, coke, soft carbon, hard carbon, pitch-based carbon fiber；The conductions such as polyacene
Property high-molecular compound；Metal composite oxide and other metal oxides etc..Wherein, preferably carbonaceous material, more preferably day
The graphite such as right graphite, Delanium, expanded graphite.The content of active material in paste compound is not particularly limited, generally
For 10~95 weight %, preferably 20~80 weight %, more preferably 35~65 weight %.
The average grain diameter of active material is not particularly limited, preferably 1~100 μm, more preferably 3~50 μm, further
Preferably 5~25 μm.It is explained, the average grain diameter of active material, which uses, passes through laser diffraction formula particle size distribution (laser
Diffraction scattering method) and the value of measure.
For the active material in negative electrode slurry composition and the containing ratio of adhesive, relative to active material
100 parts by weight, foregoing negative pole adhesive with solid constituent conversion be usually 0.1~10 parts by weight, preferably 0.5~5 weight
Measure part, particularly preferably 1~4 parts by weight.During the too high levels of negative pole adhesive, internal resistance can increase.On the other hand, its
When very few, exist can not obtain desired cohesive force, negative pole becomes the tendency that unstable, charge/discharge cycle characteristics reduce.
Negative electrode slurry composition can contain other additives in addition to above-mentioned active material, negative pole adhesive.
As other additives, can enumerate such as conductive auxiliary agent, support salt (lithium salts).For the match ratio of these compositions, close
, can also be by appropriate with reference on seeing known to lithium rechargeable battery in the match ratio as known in general scope
Solve and be adjusted.
Conductive auxiliary agent refers to the complex coordinated to improve electric conductivity.As conductive auxiliary agent, can enumerate：The carbon such as graphite
Powder；Carbon fibers such as gas-phase growth of carbon fibre (VGCF) etc., the preferably particle diameter such as acetylene black, Ketjen black are number nm~tens of nm or so
Micropowder end.The use level of conductive auxiliary agent is 1~10 weight % preferably with respect to total quality of active material layer.
And then consider workability when negative pole makes etc., it can also be adjusted according to viscosity, the adjustment of adhesive solids composition
The purpose of add solvent, prepare negative electrode slurry composition.As above-mentioned solvent, can use for example：N- crassitudes
The alcohol such as acid amides series solvent, methanol, ethanol, the higher alcohols such as ketone (NMP), dimethylformamide, dimethyl acetamide, NMF
Series solvent.
Negative pole can utilize stirring with the mixing of adhesive, active material and the additive, solvent that use as needed
Machine, deaeration machine, ball mill, high pressure homogenizer etc..In addition, the preparation of negative electrode slurry composition is preferably carried out under reduced pressure.By
This, can prevent from producing bubble in obtained active material layer.
3. lithium ion secondary battery cathode
The negative electrode slurry composition that lithium ion secondary battery negative pole can be prepared as described above by being coated with the current collector
And it is dried and manufactures.Preferably pressurizeed after coating and drying as needed and improve density.
As the collector for negative pole, the thing of the collector for the negative pole for being used as lithium rechargeable battery can be used
Matter.Specifically, it is desirable in the potential range that negative pole (carbon electrode) works in electrochemistry it is inert metal, therefore, can
Use the metal foils such as copper, nickel, etching metal foil, expanding metal etc..
By being coated with negative electrode slurry composition on this collector and being dried, negative electrode layer can be formed.As
The method of negative electrode slurry composition is coated with the current collector, can be enumerated：Doctor blade method, reverse roll method, comma rod method, intagliotype,
Air knife method etc..In addition, the condition of the drying process as the coated film of negative electrode slurry composition, treatment temperature is usually 20~
250 DEG C, preferably 50~150 DEG C.In addition, processing time is usually 1~120 minute, preferably 5~60 minutes.
The thickness (thickness of the one side of coating layer) of active material layer is usually 20~500 μm, preferably 25~300 μm,
More preferably 30~150 μm.
4. lithium rechargeable battery
The lithium rechargeable battery for possessing the negative pole made as described above is illustrated.
As positive pole, it is not particularly limited, known in general positive pole can be combined.
As positive active material, can use for example：Olivine-type LiFePO4, cobalt acid lithium, LiMn2O4, lithium nickelate,
Ternary system nickle cobalt lithium manganate, lithium nickel cobalt aluminium composite oxide etc..
As the collector of positive pole, can enumerate：The metal materials such as aluminium, copper, nickel, tantalum, stainless steel, titanium, can be according to conduct
The species of the electrical storage device of purpose is suitably selected and used.
As electrolyte, the known aprotic polar solvent for dissolving lithium salts is widely used.For example, in carbonic acid Asia second
Contain the carbonic acid as low coefficient of viscosity solvent in the cyclic carbonate such as ester, propylene carbonate system high-k, high boiling solvent
The rudimentary linear carbonate such as dimethyl ester, ethyl methyl carbonate, diethyl carbonate and use.Specifically, can enumerate：Carbonic acid Asia second
Ester, vinylene carbonate, trifluoro propylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, carbonic acid ethyl first
Ester, methyl carbonate propyl ester, isobutyl carbonate methyl, ethyl carbonate propyl ester, carbonic acid isopropyl ethyl ester, carbonic acid butyl methyl esters, carbonic acid
Butyl ethyl ester, dipropyl carbonate, 1,2- dimethoxy-ethanes, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofurans, ring fourth
Sulfone, 3- methyl sulfolanes, 2,4- dimethylsulfolanes, 1,3- dioxolanes, methyl acetate, ethyl acetate, methyl formate, formic acid
Ethyl ester etc..These materials are preferably mixed and used.
As the lithium salts of electrolyte, LiClO is used4、LiPF6、LiBF4、LiAsF6, the inorganic salts such as LiCl, LiBr；
LiCF3SO3、LiN(SO2CF3))2、LiN(SO2C2F5)2、LiC(SO2CF3)3、LiN(SO3CF3))2Deng organic salt etc. as non-aqueous
The material that the electrolyte of electrolyte is commonly used.Wherein, preferably using LiPF6、LiBF4Or LiClO4。
As dividing plate, it is not particularly limited, non-woven fabrics, porous membrane of polyolefin etc. can be used.
As the structure of secondary cell, it is not particularly limited, lamination-type (platypelloid type) battery, convoluted (cylinder can be enumerated
Type) battery etc., it is readily applicable to currently known any form and structure.In addition, in lithium rechargeable battery
The connection form (electrode structure) of electricity, it is readily applicable to the bipolar of the internal battery of connecting-type side by side and inside connecting-type in upright arrangement
Type battery it is any.
The lithium rechargeable battery obtained as described above is held based on the negative pole adhesive using the present invention, initial discharge
Amount is high, and with stable output characteristics.
【Embodiment】
Hereinafter, embodiment and comparative example are enumerated, in further detail the explanation present invention.It is explained, it is of the invention and unlimited
Due to following embodiment.
(synthesis example 1)
The synthesis of the micro- monomer of 1-1. PAAs (the carboxylic micro- monomer of hydrophily)
Water 18.00g, the water of polyacrylic acid 40% are sequentially loaded into the reaction vessel for having agitating device, air cooling pipe and thermometer
Solution 53.20g (acrylic acid units 295mmol, number-average molecular weight 5,300), the aqueous solution 24.60g of sodium hydroxide 48% and first
Base glycidyl acrylate 4.20g (29.5mmol), is heated and temperature is warming up to 40 DEG C.The temperature of reaction solution is existed
Kept for 6 hours at 40 DEG C, obtain the micro- monomer solution of the Sodium Polyacrylate (weight of solid component concentration 32 with methylacryloyl
Measure %).After reaction terminates, carry out reprecipitation for several times with acetone and refine the micro- monomer of polyacrylic acid.By obtained Sodium Polyacrylate
The number-average molecular weight that the GPC (liquid chromatography) of micro- monomer is obtained is 5,600.
Copolymerization (the system of core-crown type high molecular particle of the micro- monomer of 1-2. PAAs and 2-Ethylhexyl Methacrylate
Make)
Then, it is sequentially loaded into above-mentioned Sodium Polyacrylate in the reaction vessel for having agitating device, backflow cooler and thermometer
Micro- monomer solution 22.16g [being 65mmol (being obtained by preceding charging) as acrylic acid units repeat unit], methacrylic acid 2- second
The own ester 12.87g (65mmol) of base and water 63.45g, are warming up to 70 DEG C.20 weight % of ammonium persulfate are added in the mixture
Aqueous solution 1.50g (1.31mmol), it is copolymerized 6 hours, obtain milky dispersion liquid (the weight % of solid component concentration 20).
The average grain diameter of the high molecular particle of the obtained hydrophily hat chain having containing carboxylic acid sodium is 190nm.
(synthesis example 2)
The copolymerization (making of core-crown type high molecular particle) of the micro- monomer of PAA and 2-Ethylhexyl Methacrylate
The micro- monomer solution of Sodium Polyacrylate is changed to 46.67g [being 130mmol as acrylic acid units repeat unit], by first
Base 2-EHA is changed to 6.44g (33mmol), and water is changed into 45.39g, in addition, same with synthesis example 1-2
Operate sample, obtain milky dispersion liquid (the weight % of solid component concentration 22).What is obtained has the hydrophily containing carboxylic acid sodium
The average grain diameter for being preced with the high molecular particle of chain is 250nm.
(synthesis example 3)
The synthesis of the micro- monomer of 3-1. PAAs (the carboxylic micro- monomer of hydrophily)
Using the aqueous solution of polyacrylic acid 40% of number-average molecular weight 16,500, in addition, operated in the same manner as synthesis example 1-2,
Obtain the micro- monomer solution of Sodium Polyacrylate (the weight % of solid component concentration 32) with methylacryloyl.Obtained polypropylene
The number-average molecular weight obtained using GPC (liquid chromatography) of the sour micro- monomer of sodium is 17,000.
Copolymerization (the system of core-crown type high molecular particle of the micro- monomer of 3-2. PAAs and 2-Ethylhexyl Methacrylate
Make)
Using the micro- monomer solution of Sodium Polyacrylate synthesized in synthesis example 3-1, in addition, operated in the same manner as synthesis example 1-2,
Obtain milky dispersion liquid (the weight % of solid component concentration 20).The high score of the obtained hydrophily hat chain having containing carboxylic acid sodium
The average grain diameter of sub- particulate is 320nm.
(synthesis example 4)
The synthesis of 4-1. sodium carboxymethylcelluloses (following, CMCNa) micro- monomer (the carboxylic micro- monomer of hydrophily)
The CMC10.00g of water 89.08g, powder is sequentially loaded into the reaction vessel for having agitating device, air cooling pipe and thermometer
(carboxyl 30mmol, number-average molecular weight 15,600), the aqueous solution 0.50g of sodium hydroxide 48% and methyl propenoic acid glycidyl
Ester 0.42g (3.0mmol), is heated and temperature is warming up to 40 DEG C.The temperature of reaction solution is kept for 6 hours at 40 DEG C,
Obtain the micro- monomer solutions of CMCNa (the weight % of solid component concentration 10) with methylacryloyl.After reaction terminates, acetone is used
Reprecipitation for several times is carried out, the micro- monomers of CMCNa are refined.The obtained micro- monomers of CMCNa are asked using GPC (liquid chromatography)
The number-average molecular weight gone out is 16,000.
The copolymerization (making of core-crown type high molecular particle) of the micro- monomers of 4-2.CMCNa and 2-Ethylhexyl Methacrylate
Then, the micro- monomers of above-mentioned CMCNa are sequentially loaded into the reaction vessel for having agitating device, backflow cooler and thermometer
Solution 50.00g [being 22mmol (being obtained by preceding charging) as glucose unit repeat unit], 2-Ethylhexyl Methacrylate
4.37g (22mmol) and water 44.13g, is warming up to 70 DEG C.The 20 weight % aqueous solution of ammonium persulfate are added in the mixture
1.50g (1.31mmol), it is copolymerized 6 hours, obtain milky dispersion liquid (the weight % of solid component concentration 10).Obtain
The average grain diameter of high molecular particle with CMCNa hat chains is 200nm.
(comparing synthesis example 1)
30 weight % water of PAA are sequentially loaded into the reaction vessel for having agitating device, backflow cooler and thermometer
Solution 21.94g (70mmol), neopelex 10 weight % aqueous solution 10.00g, methacrylic acid 2- ethyl hexyls
Ester 13.86g (70mmol) and water 52.70g, is warming up to 70 DEG C.The 20 weight % for adding ammonium persulfate in the mixture are water-soluble
Liquid 1.50g (1.31mmol).It is copolymerized 6 hours, obtain milky dispersion liquid (the weight % of solid component concentration 22).Obtain
The average grain diameter of emulsion be 230nm.
Embodiment 1
Using the negative pole adhesive of synthesis example 1, the lithium rechargeable battery that the present invention is made by following method evaluates use
Half-cell.It is explained, as the material of evaluation half-cell, uses following material.
Negative electrode active material：Natural graphite powder
To pole：Lithium metal foil
Conductive auxiliary agent：Micropowder end
Tackifier：Sodium carboxymethylcellulose (CMCNa)
Electrolyte：Lithium lithium phosphate (the LiPF of 1mol/L6The mixed liquor of)/ethylene carbonate (EC) and diethyl carbonate (DEC)
(EC：DEC (volume ratio)=1：1)
Dividing plate：Cellulose-based dividing plate
Collector：Copper foil
The 2 weight % CMCNa aqueous solution is prepared, with the negative pole of natural graphite powder, micropowder end, CMCNa and synthesis example 1
Turn into 95 with the dried electrode ratio of components (weight ratio) of adhesive：3：1：The mode of 1 ratio is mixed, and makes slurry
Material.Pure water is suitably added in the slurry after obtaining uniform slurry, using scraper for coating in copper foil, is done at 100 DEG C
Dry 20 minutes.The electrode is cut into 16mm circle, under 80 DEG C of temperature atmosphere, 10-1Dry 24 hours, obtain under Pa decompression
To the Carbon anode as object.Configure Carbon anode and to pole lithium metal foil, dividing plate configured between two electrodes, inject electrolyte,
Make 2 pole formula evaluation half-cells.
Embodiment 2
Negative pole is changed to the adhesive of synthesis example 2 with adhesive, in addition, operated similarly to Example 1, makes 2 poles
Formula evaluation half-cell.
Embodiment 3
Negative pole is changed to the adhesive of synthesis example 3 with adhesive, in addition, operated similarly to Example 1, makes 2 poles
Formula evaluation half-cell.
Embodiment 4
Negative electrode binder is changed to the adhesive of synthesis example 4, in addition, operated similarly to Example 1, makes 2 pole formulas
Evaluation half-cell.
Embodiment 5
Without using tackifier (CMCNa), negative electrode binder is changed to the adhesive of synthesis example 4, natural graphite powder, carbon is micro-
Powder and the adhesive of synthesis example 4 are with the dried electrode group of the adhesive of natural graphite powder, micropowder end and synthesis example 4
Turn into 95 into than (weight ratio)：3：The mode of 2 ratio is mixed, and makes slurry, in addition, similarly to Example 1
Operation, make 2 pole formula evaluation half-cells.
Comparative example 1
Negative pole is changed to SBR (milky white liquid, the weight % of solid component concentration 40) with adhesive, in addition, with implementation
Example 1 similarly operates, and makes 2 pole formula evaluation half-cells.
Comparative example 2
Negative pole is changed to the emulsion that compares synthesis example 1 with adhesive, in addition, operates similarly to Example 1, makes 2
Pole formula evaluation half-cell.
Comparative example 3
By negative pole with adhesive be changed to aqueous sodium polyacrylate (the weight % of solid component concentration 40, number-average molecular weight 16,
500), in addition, operate similarly to Example 1, make 2 pole formula evaluation half-cells.
[measure example 1：The speed characteristic of lithium ion battery]
Relative to embodiment 1~5 and the evaluation half-cell of comparative example 1~3, in 0.05~1.2V operating voltage range with
After 0.1C 1 circulation of current density, discharge and recharge is carried out with each 5 circulations of the current density of 1C, 3C, 5C, 8C and 10C speed,
Finally return back to 1C speed and carry out 5 cycle charge-discharges, study the discharge capacity under each current density.By with each current density
Percentage (%) obtained by the discharge capacity divided by initial stage (0.1C speed) discharge capacity of 5th circulation is set to volume conservation rate.Will
The results are shown in table 1 and Fig. 2.Capability retention is higher, represents that speed characteristic is higher.
【Table 1】
Each composition in table 1 is as described below.
SBR：Styrene-butadiene latex
EHMA：2-Ethylhexyl Methacrylate
AAcNa：PAA
PAAcNa：Sodium Polyacrylate
CMCNa：Sodium carboxymethylcellulose
From table 1 and Fig. 2：2 pole formula evaluations of embodiment with half-cell compared with the half-cell of comparative example, in high-speed
It is lower to keep high capacity.
[measure example 2：The impedance of lithium ion battery]
On the embodiment 1 and the half-cell of comparative example 1 used in measure example 1, and then, to open loop voltage in potential amplitude
Based on AC Impedance Measurements is carried out under conditions of 10mV, a-c cycle scope 100kHz~10mHz.The impedance of real number will be taken in X-axis
(Z '), the Nyquist of impedance (Z ") of imaginary number is taken in Y-axis to mark and draw (Cole-Cole plottings) and be shown in Fig. 3.
As shown in Figure 3：For the resistance value of the battery of embodiment 1, compared with the battery of comparative example 1, resistance value is low.
Symbol description
The 1 carboxylic micro- monomer of hydrophily
1a acrylic acid units
1b contains the side chain of vinyl
2 hydrophobic monomers
3 hydrophobic core portions
4 hydrophily bizets
5 high molecular particles
Claims (6)
1. a kind of adhesive, its be the lithium containing the dispersion liquid that core-crown type high molecular particle is dispersed with aqueous dispersion medium from
Sub- secondary battery negative pole adhesive, wherein,
The core-crown type high molecular particle has following structure：By the construction unit shape from the micro- monomer of carboxylic hydrophily
Into hydrophily bizet surround around the hydrophobic core portion formed by the construction unit from hydrophobic monomer.
2. adhesive according to claim 1, wherein,
The core-crown type high molecular particle is free to make the micro- monomer of the carboxylic hydrophily and hydrophobic monomer progress
The high molecular particle that base is polymerized,
The micro- monomer of carboxylic hydrophily is carboxylic high-molecular compound and intramolecular is had polymerism reactive group
Group and with carboxyl reaction and form micro- monomer for forming of compound reaction of both functional groups of covalent bond.
3. adhesive according to claim 2, wherein,
The intramolecular has polymerism reactive group and forms the chemical combination of both functional groups of covalent bond with carboxyl reaction
Thing is the chemical combination selected from compound, the compound that following formulas (2) represent and formula (3) expression represented by following formulas (1)
At least one kind of compound in the group that thing is formed,
In formula, R1Represent hydrogen atom or methyl, Q1Oxygen atom or-NH- are represented,
In formula, R2Represent hydrogen atom or methyl, Q2Oxygen atom or the integer of-NH-, n expression 1~4 are represented,
In formula, R3Represent hydrogen atom or methyl, R4Represent hydrogen atom, the alkyl or halogen atom of carbon number 1~4, X1Represent that halogen is former
Son.
4. a kind of lithium ion secondary battery negative pole paste compound, its contain lithium according to any one of claims 1 to 3 from
Sub- secondary battery negative pole adhesive and active material.
5. a kind of lithium ion secondary battery negative pole, it is to be coated with the lithium rechargeable battery described in claim 4 on the current collector
Negative electrode slurry composition is simultaneously dried and formed.
6. a kind of lithium rechargeable battery, it contains the lithium ion secondary battery negative pole described in claim 5.
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| JP2015217331 | 2015-11-05 | ||
| PCT/JP2016/081903 WO2017077940A1 (en) | 2015-11-05 | 2016-10-27 | Binder for negative electrodes of lithium ion secondary batteries, slurry composition for negative electrodes, negative electrode, and lithium ion secondary battery |
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| CN108847488A (en) * | 2018-06-14 | 2018-11-20 | 汕头市鲁汕化工原料有限公司 | Lithium ion secondary battery active material adhesive |
| CN112002903A (en) * | 2020-08-24 | 2020-11-27 | 湖北亿纬动力有限公司 | Oily binder and application thereof |
| CN116987466A (en) * | 2023-09-22 | 2023-11-03 | 蜂巢能源科技股份有限公司 | Modified adhesive and preparation method thereof, negative plate, lithium ion battery and preparation method thereof |
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| CN109935830B (en) * | 2017-12-15 | 2021-08-20 | 浙江中科立德新材料有限公司 | Preparation method of lithium ion battery silicon-carbon negative electrode plate based on modified gelatin binder |
| CN111699574B (en) * | 2018-03-07 | 2023-05-05 | 日本瑞翁株式会社 | Binder composition for nonaqueous secondary battery electrode, method for producing same, slurry composition for nonaqueous secondary battery electrode, electrode for nonaqueous secondary battery, and nonaqueous secondary battery |
| EP3780186A4 (en) * | 2018-03-27 | 2022-01-26 | Zeon Corporation | Binder composition for secondary cell, slurry composition for secondary cell functional layer, secondary cell member, secondary cell, and method for manufacturing slurry composition for secondary cell negative electrode |
| CN117425985A (en) * | 2021-05-28 | 2024-01-19 | 株式会社力森诺科 | Nonaqueous secondary battery electrode binder and nonaqueous secondary battery electrode |
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|---|---|---|---|---|
| CN108847488A (en) * | 2018-06-14 | 2018-11-20 | 汕头市鲁汕化工原料有限公司 | Lithium ion secondary battery active material adhesive |
| CN108847488B (en) * | 2018-06-14 | 2021-02-26 | 汕头市鲁汕化工原料有限公司 | Active material binder for lithium ion secondary battery |
| CN112002903A (en) * | 2020-08-24 | 2020-11-27 | 湖北亿纬动力有限公司 | Oily binder and application thereof |
| CN112002903B (en) * | 2020-08-24 | 2022-01-14 | 湖北亿纬动力有限公司 | Oily binder and application thereof |
| CN116987466A (en) * | 2023-09-22 | 2023-11-03 | 蜂巢能源科技股份有限公司 | Modified adhesive and preparation method thereof, negative plate, lithium ion battery and preparation method thereof |
| CN116987466B (en) * | 2023-09-22 | 2024-01-30 | 蜂巢能源科技股份有限公司 | Modified adhesive and preparation method thereof, negative plate, lithium ion battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017077940A1 (en) | 2017-05-11 |
| KR102570761B1 (en) | 2023-08-25 |
| TW201721945A (en) | 2017-06-16 |
| CN107710470B (en) | 2021-01-22 |
| TWI709275B (en) | 2020-11-01 |
| KR20180075436A (en) | 2018-07-04 |
| JPWO2017077940A1 (en) | 2018-08-30 |
| JP6795814B2 (en) | 2020-12-02 |
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