CN109786747A - Lithium ion battery binder and its preparation method and application - Google Patents
Lithium ion battery binder and its preparation method and application Download PDFInfo
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- CN109786747A CN109786747A CN201811643336.4A CN201811643336A CN109786747A CN 109786747 A CN109786747 A CN 109786747A CN 201811643336 A CN201811643336 A CN 201811643336A CN 109786747 A CN109786747 A CN 109786747A
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Abstract
The invention belongs to technical field of lithium ion, more particularly to a kind of lithium ion battery, it include the non-linear multi-arm homopolymer being made of polynary small molecule parent nucleus and the polyacrylic acid or polyacrylate branch chain arm that are connected on the polynary small molecule parent nucleus, due to nonlinear polyacrylic acid or polyacrylate multi-arm structure, the flexibility of binder is increased, and this nonlinear organization has both various dimensions and efficiently bonds and water-soluble advantage.Relative to linear polyacrylic binder, the crisp defect of molecularity is improved to a certain extent.It solves the problems, such as cause pole piece to crack because of binder itself brittleness in circulating battery, peel off etc. to lead to poor circulation.
Description
Technical field
The invention belongs to technical field of lithium ion more particularly to a kind of lithium ion battery binder and preparation method thereof
And application.
Background technique
Lithium ion battery meets people to protection environment and slows down energy crisis as a kind of environmentally protective energy storage technology
Pursuit, by more and more extensive research, production and application.Improve the energy density lithium ion battery always of lithium ion battery
The hot and difficult issue of technical field research.Silicon based anode material is since its theoretical capacity can achieve 4200mAh/g, relative to biography
(theoretical capacity (372mAh/g) has bigger grind in terms of improving lithium ion battery energy density to the carbon-based negative electrode material of the graphite of system
Study carefully space, be one of the negative electrode material of current most study, is also most hopeful to substitute the novel high-energy density cathode of graphite
Material.
Greatest problem existing for silicon based anode material first is that: due to the biggish Volumetric expansion of silicon based anode material
(~300%, the expansion of graphite material is only~10%), lithium ion battery is during removal lithium embedded, it may occur that great volume becomes
Change, pole piece variation is to cause variation or deterioration, such as crackle, peeling of pole piece structure etc., to influence battery performance, especially
It is the cycle performance for influencing battery.Binder can bond together active material etc., so that the stabilization of pole piece structure is kept,
Big volume change needs the cohesive force compared with wholesale to disinthibite or adapt to, so relative to the carbon-based negative electrode material of existing graphite, silicon
Base negative electrode material has higher requirement to binder system.
Currently, rapid development has been obtained with binder in silicon-based anode, and its type is also more and more.It is reported
Silicium cathode adhesive mainly includes sodium carboxymethylcellulose, polyacrylic acid epoxy-type, sodium alginate, chitosan derivatives, cross-linking type
The binders such as bonding.Wherein, cross-linking type binder because have three-dimensional network bring various dimensions efficiently bond and by pass
Note.However, cross-linking type binder also faces the realistic problems such as preparation process complexity.Polyacrylie-type binder, due to polymer
It containing a large amount of-COOH in strand, is applied in negative electrode binder, the strong hydrogen bond action of a large amount of-COOH brings,
Make it have preferable bonding behavior, but because self-molecules present chain is relatively regular and toughness is insufficient, binder will often occur
It destroys (binder molecular breakdown), pole piece can be caused to crack, peel off because of itself brittleness in circulating battery, thus
Influence the cycle performance of battery.
Summary of the invention
The embodiment of the present invention is designed to provide a kind of lithium ion battery binder, it is intended to solve existing polyacrylic
Linear binder toughness due to self-molecules present chain is relatively regular is insufficient, can lead because of bonding agent itself brittleness in circulating battery
Pole piece is caused the technical issues of of leading to poor circulation such as to crack, peel off.
The another object of the embodiment of the present invention is to provide a kind of preparation method of lithium ion battery bonding agent.
A further object for the embodiment of the present invention is to provide a kind of lithium ion battery.
In order to achieve the above-mentioned object of the invention, The technical solution adopted by the invention is as follows:
A kind of lithium ion battery binder, the lithium ion battery binder include by polynary small molecule parent nucleus and connection
The non-linear multi-arm homopolymer of polyacrylic acid or polyacrylate branch chain arm composition on the polynary small molecule parent nucleus.
Correspondingly, a kind of preparation method of lithium ion battery binder, comprising the following steps:
Polynary small molecule, initiator and monomer are obtained, the monomer is selected from acrylic monomer or non-acrylic monomer；
By the polynary small molecule, initiator and the monomer mixed dissolution in liquid phase medium, polymerization reaction is carried out, is obtained thick
Product；
When the monomer is acrylic monomer, the crude product is purified, it is viscous to obtain nonlinear lithium ion battery
Tie agent；When the monomer is non-acrylic monomer, after purification by the crude product, conversion processing is carried out, purifies, obtains again
Obtain nonlinear lithium ion battery binder.
Preferably, the polynary small molecule is selected from: the halides of small molecule polyol or small molecule polyol, described small
Molecular polylol is at least containing there are three the small molecule polyols of hydroxyl.
Preferably, the acrylic monomer is selected from acrylic monomers or Acrylates monomer；And/or it is described non-
Acrylic monomer is selected from acrylic ester monomer or acrylonitrile monomer.
Preferably, when the polynary small molecule is small molecule polyol, the initiator is selected from: potassium peroxydisulfate, over cure
At least one of sour ammonium, ammonium ceric nitrate, anhydrous calcium chloride, hydrogen peroxide；
When the polynary small molecule is the halides of small molecule polyol, the initiator is selected from: the sub- second of pentamethyl two
Base triamine/copper bromide, tetramethylethylenediamine/copper bromide, hexamethyl trien/copper bromide, three (N, N- dimethylaminos
Ethyl) amine/copper bromide, five methyl diethylentriamine/copper chloride, tetramethylethylenediamine/copper chloride, hexamethyl triethylene four
At least one of amine/copper chloride, three (N, N- dimethyl aminoethyl) amine/copper chlorides.
Preferably, when the polynary small molecule is small molecule polyol, the liquid phase medium is selected from: N, N- dimethyl methyl
It is one or more of in amide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide or aqueous solvent；
When the polynary small molecule is the halides of small molecule polyol, the liquid phase medium is selected from: N, N- dimethyl
It is one or more of in formamide, N-Methyl pyrrolidone or DMAC N,N' dimethyl acetamide.
Preferably, the polynary small molecule and the molar ratio of the monomer are 1:(500~10000)；And/or described draw
Send out 1~2 multiple that agent dosage is reaction site molal quantity in the polynary small molecule.
Preferably, when the polynary small molecule is small molecule polyol, the condition of the polymerization reaction are as follows: be in temperature
Under conditions of 30 DEG C~90 DEG C, it is stirred to react 12 hours~24 hours with the mixing speed of 300~500rpm；When described polynary small
When molecule is the halides of small molecule polyol, the condition of the polymerization reaction are as follows: under dry inert gas atmosphere, in temperature
Under conditions of 30 DEG C~90 DEG C, it is stirred to react 12 hours~24 hours with the mixing speed of 300~500rpm.
Preferably, the method for the purifying is extraction；And/or
When the monomer is acrylic acid nitrile monomer, the method for the conversion processing is basic hydrolysis；When the monomer is
When propylene esters monomer, the method for the conversion processing is ester decomposition；And/or
The method of the repurity is dialysis.
A kind of lithium ion battery, the lithium ion battery include above-mentioned lithium ion battery binder；And/or the lithium
Ion battery includes above-mentioned electrodes of lithium-ion batteries.
Lithium ion battery binder provided by the invention includes by polynary small molecule parent nucleus and to be connected to described polynary small
The non-linear multi-arm homopolymer of polyacrylic acid or polyacrylate branch chain arm composition on molecule parent nucleus, due to nonlinear poly- third
Olefin(e) acid or polyacrylate multi-arm structure, increase the flexibility of binder, and to have both various dimensions efficient for this nonlinear organization
Bonding and water-soluble advantage.Relative to linear polyacrylic binder, it is crisp that molecularity is improved to a certain extent
Defect, efficiently solve causes pole piece to crack, peels off etc. to cause to follow in circulating battery because of binder itself brittleness
The problem of ring performance difference.
The preparation method of lithium ion battery binder provided by the invention, using polynary small molecule as core, in initiator
Under effect, grow polyacrylic acid or polyacrylate branch in the heart in polynary small molecular core, obtain the nonlinear lithium of multi-arm from
Sub- battery binder.The preparation method is easy to operate, at low cost, is easy to industrialization production, can promote electrodes of lithium-ion batteries
Business application.
Lithium ion battery provided by the invention, due to containing it is above-mentioned have various dimensions efficiently bond, water solubility and it is flexible
Non-linear lithium ion battery binder, and/or, the electrodes of lithium-ion batteries containing above-mentioned performance and stable structure, therefore, this hair
The lithium ion battery of bright offer has preferable cyclical stability and safety.
Detailed description of the invention
Fig. 1 is the molecular structure for the non-linear lithium ion battery binder that the embodiment of the present invention 1 provides.
Fig. 2 is the molecular structure for the non-linear lithium ion battery binder that the embodiment of the present invention 2 provides.
Fig. 3 is the core for the non-linear lithium ion battery binder molecule hydrolysis front and back characteristic peak that the embodiment of the present invention 1 provides
Magnetic resonance hydrogen spectrogram.
Fig. 4 is the core for the non-linear lithium ion battery binder molecule hydrolysis front and back characteristic peak that the embodiment of the present invention 2 provides
Magnetic resonance hydrogen spectrogram
Fig. 5 is the CR2016 button half-cell 1 that the embodiment of the present invention 3 provides and the CR2016 button half that comparative example 1 provides
The cyclical stability test chart of battery comparative example 1.
Fig. 6 is the CR2016 button half-cell 2 that the embodiment of the present invention 4 provides and the CR2016 button half that comparative example 2 provides
The cyclical stability test chart of battery comparative example 2.
Specific embodiment
To keep the purpose, technical solution and technical effect of the embodiment of the present invention clearer, below in conjunction with of the invention real
The attached drawing in example is applied, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.In conjunction with the embodiment in the present invention, ordinary skill
Personnel's every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that, term " first ", " second " are used for description purposes only, and cannot
It is interpreted as indication or suggestion relative importance or implicitly indicates the quantity of indicated technical characteristic.Define as a result, " the
One ", the feature of " second " can explicitly or implicitly include one or more of the features.In the description of the present invention,
The meaning of " plurality " is two or more, unless otherwise specifically defined.
The embodiment of the invention provides a kind of lithium ion battery binder, the lithium ion battery binder includes by more
First small molecule parent nucleus and the polyacrylic acid being connected on the polynary small molecule parent nucleus or polyacrylate branch chain arm form non-
Linear multi-arm homopolymer.
Lithium ion battery binder provided in an embodiment of the present invention includes by polynary small molecule parent nucleus and to be connected to described
The non-linear multi-arm homopolymer of polyacrylic acid or polyacrylate branch chain arm composition on polynary small molecule parent nucleus, due to non-linear
Polyacrylic acid or polyacrylate multi-arm structure, increase the flexibility of binder, and this nonlinear organization has both multidimensional
Degree efficiently bonds and water-soluble advantage.Relative to linear polyacrylic binder, molecule is improved to a certain extent
The crisp defect of property, efficiently solve causes pole piece to crack, peel off in circulating battery because of binder itself brittleness
The problem of leading to poor circulation.
As a preferred embodiment, the polynary small molecule is selected from: small molecule polyol or small molecule polyol it is halogenated
Object, the small molecule polyol are at least containing there are three the small molecule polyols of hydroxyl.The polynary small molecule is containing multiple
The small molecule in polymerization reaction site.Wherein, the halides of small molecule polyol and small molecule polyol are containing multiple polymerizations
The small molecule of reaction site can be provided as the offer multidigit point of the growth of branch chain arm.With the small molecule at least containing three hydroxyls
The halides of polyalcohol or small molecule polyol are core, provide at least three growth sites for the growth of branch chain arm, are formed extremely
Few three chain arm binder molecular structures.Polynary small molecule is selected from small molecule polyol in the embodiment of the present invention or small molecule is more
The halides of first alcohol, small molecule core ensure that binder product is homopolymer, avoid macromolecular core and generate copolymer simultaneously
Introduce other components, disturbing reaction system.It is highly preferred that the small molecule polyol is at least containing there are three small points of terminal hydroxy group
Sub- polyalcohol, the small molecule polyol containing terminal hydroxy group are more advantageous to the non-linear binder of multi-arm to form homopolymerization.
In some embodiments, small molecule polyol is selected from: trimethylolpropane, and the substances such as pentaerythrite, glycerine are
The growth of branch chain arm provides three or more growth sites.Preferably, the small molecule polyol is selected from: trimethylolpropane,
Pentaerythrite.Wherein, trimethylolpropane is common chain extender, and fusing point is low, has 3 methylols in molecular structure, can be
The growth of branch chain arm provides three growth sites, forms the non-linear binder of three branches.Pentaerythrite is containing there are four equivalent
Methylol, the symmetry with height, can provide four growth sites, and between branch chain arm and each site for the growth of branch chain arm
Binding force it is identical.
In some embodiments, the halides of small molecule polyol can be different by the small molecule polyol and 2- bromo
Butyryl bromide reacts the polynary bromo-derivative of small molecule of preparation under triethylamine effect.
As a preferred embodiment, the monomer is selected from: acrylic monomers, Acrylates monomer, acrylic ester monomer,
At least one of acrylonitrile monemer.The embodiment of the present invention passes through acrylic monomers, Acrylates monomer, esters of acrylic acid
The monomers such as monomer, acrylonitrile monemer grow into polyacrylic acid or polyacrylate branch chain arm in the polynary small molecule of core.
As a preferred embodiment, lithium ion battery binder provided in an embodiment of the present invention is preferably applied to silicon-based anode
In material, since lithium ion battery binder provided in an embodiment of the present invention contains the bonding agent molecule of nonlinear organization, it can fit
The expansion of silicon based anode material is answered, the capacity that can significantly improve silicon-based anode lithium ion battery plays and cycle performance.
Lithium ion battery binder described in the embodiment of the present invention can be prepared by following methods.
The embodiment of the invention provides a kind of preparation methods of lithium ion battery binder, comprising the following steps:
S10. polynary small molecule, initiator and monomer are obtained, the monomer is selected from acrylic monomer or non-acrylic compounds
Monomer；
S20. by the polynary small molecule, initiator and the monomer mixed dissolution in liquid phase medium, polymerization reaction is carried out, is obtained
Obtain crude product；
S30. when the monomer is acrylic monomer, the crude product is purified, nonlinear lithium-ion electric is obtained
Pond binder；When the monomer is non-acrylic monomer, after purification by the crude product, conversion processing is carried out, it is pure again
Change, obtains nonlinear lithium ion battery binder.
The preparation method of lithium ion battery binder provided in an embodiment of the present invention is being drawn using polynary small molecule as core
Under the action of sending out agent, polyacrylic acid or polyacrylate branch are grown in the heart in polynary small molecular core, obtains the non-linear of multi-arm
Lithium ion battery binder.The preparation method is easy to operate, at low cost, raw material sources are wide, is easy to industrialization production, can promote
The business application of electrodes of lithium-ion batteries.
Specifically, in above-mentioned steps S10, polynary small molecule, initiator and monomer are obtained, the monomer is selected from acrylic compounds
Monomer or non-acrylic monomer.
As a preferred embodiment, the polynary small molecule is selected from: small molecule polyol or the small molecule polyol
Halides, the small molecule polyol are at least containing there are three the small molecule polyols of terminal hydroxy group.Small molecule polyol can provide
The multidigit point of branch chain arm growth.With at least containing three terminal hydroxy groups small molecule polyol or the small molecule polyol it is halogenated
Object is core, provides at least three growth sites for the growth of branch chain arm, forms at least three chain arm binder molecular structures.When
When the polynary small molecule is small molecule polyol, subsequent polymerisation reaction system is that redox free radical system polymerize, small point
Sub- polyalcohol is used as reducing agent in system, under the action of oxidant (initiator), redox reaction occurs, is produced from
By base, initiated polymerization；When the polynary small molecule is the halides of small molecule polyol, subsequent polymerisation reaction system is
It is anti-to cause polymerization under the catalytic action of initiator for atom transfer radical polymerization (ATRP), the halides of small molecule polyol
It answers.The monomer is selected from acrylic monomer or non-acrylic monomer, and acrylic monomer and non-acrylic monomer are drawing
Under the action of sending out agent, the non-linear branched structure of multi-arm can be formed at branch chain arm by aggregation growth in polynary small molecule.
As a preferred embodiment, the acrylic monomer is selected from acrylic monomers or Acrylates monomer.Propylene
Acid monomers or acrylate monomers homopolymerization can grow polyacrylic acid directly on polynary small molecule parent nucleus by the initiation of initiator
Monomer or polyacrylic acid salt monomer form the nonlinear lithium ion battery binder of multi-arm.
As a preferred embodiment, the non-acrylic monomer is selected from acrylic ester monomer or vinyl cyanide list.Wherein,
Acrylonitrile monemer after acrylonitrile monemer polymer, can grow into polypropylene by the initiation of initiator on polynary small molecular core
Nitrile branch chain arm obtains the crude product containing a plurality of polyacrylonitrile branch chain arm；Initiation of the acrylic ester monomer by initiator, propylene
After esters of gallic acid monomer polymerization, polypropylene ester branch chain arm can be grown on polynary small molecular core, is obtained containing a plurality of polypropylene ester
The crude product of branch chain arm.
As a preferred embodiment, the acrylic ester monomer is selected from: Tert-butyl Methacrylate, methyl acrylate, and third
The monomers such as olefin(e) acid N-butyl.It is highly preferred that the acrylic ester monomer is Tert-butyl Methacrylate.
In some embodiments, the acrylic monomer is selected from acrylic monomers or Acrylates monomer；It is described
Non- acrylic monomer is selected from acrylic ester monomer or acrylonitrile monomer.
The embodiment of the present invention does not do specific restriction to initiator, polymerize as long as can cause polynary small molecule with monomer
Reaction generates the non-linear homopolymer of highly branched chain arm.As a preferred embodiment, when the polynary small molecule is that small molecule is more
When first alcohol, the initiator is selected from: at least one of potassium peroxydisulfate, ammonium persulfate, ammonium ceric nitrate, anhydrous calcium chloride, hydrogen peroxide；
When the polynary small molecule is the halides of the small molecule polyol, the initiator is selected from: pentamethyl diethylidene three
Amine/copper bromide, tetramethylethylenediamine/copper bromide, hexamethyl trien/copper bromide, three (N, N- dimethylaminoethyls
Base) amine/copper bromide, five methyl diethylentriamine/copper chloride, tetramethylethylenediamine/copper chloride, hexamethyl triethylene four
At least one of amine/copper chloride, three (N, N- dimethyl aminoethyl) amine/copper chlorides.Initiator is used in the embodiment of the present invention
The initiation polynary small molecule of core polymerize with monomer.Wherein, potassium peroxydisulfate, ammonium persulfate, ammonium ceric nitrate, anhydrous calcium chloride, double
Oxygen water is strong oxidizer initiator, can effectively cause polynary small molecule (small molecule polyol class) and monomer with reduction characteristic
Redox free radical polymerization occurs.Five methyl diethylentriamine/copper bromide, tetramethylethylenediamine/copper bromide, hexamethyl three
Ethylene tetra/copper bromide, three (N, N- dimethyl aminoethyl) amine/copper bromide, five methyl diethylentriamine/copper chloride,
Tetramethylethylenediamine/copper chloride, hexamethyl trien/copper chloride and three (N, N- dimethyl aminoethyl) amine/chlorination
Copper initiator, can effectively cause halogenated polyhydric small molecule (halides of small molecule polyol) and atom transfer freedom occurs for monomer
Base polymerization.Preferably, when the polynary small molecule is the halides of small molecule polyol, the initiator is that pentamethyl two is sub-
Ethyl triamine/copper bromide.
Specifically, in above-mentioned steps S20, the polynary small molecule, initiator and monomer are mixed in liquid phase medium, into
Row polymerization reaction obtains crude product.The embodiment of the present invention makes to grow branch in polynary small molecule by initiator initiated polymerization
Chain arm forms nonlinear multi-arm structure.
As a preferred embodiment, when the polynary small molecule is small molecule polyol, the liquid phase medium is selected from: N, N-
It is one or more of in dimethylformamide, N-Methyl pyrrolidone, DMAC N,N' dimethyl acetamide or aqueous solvent；When described polynary
When small molecule is the halides of the small molecule polyol, the liquid phase medium is selected from: n,N-Dimethylformamide, N- methyl pyrrole
It is one or more of in pyrrolidone or DMAC N,N' dimethyl acetamide.It is subsequent poly- when the polynary small molecule is small molecule polyol
Reaction system is closed as the polymerization of redox free radical system, liquid phase medium can be n,N-Dimethylformamide, N- methyl at this time
Pyrrolidones, DMAC N,N' dimethyl acetamide or water equal solvent.When the halides that the polynary small molecule is small molecule polyol
When, subsequent polymerisation reaction system is atom transfer radical polymerization (ATRP), and the halides of small molecule polyol are in initiator
Under catalytic action, initiated polymerization, liquid phase medium can be n,N-Dimethylformamide, N-Methyl pyrrolidone or N at this time,
One or more of organic solvents in N- dimethyl acetamide.Wherein, dimethylformamide energy and water and most of organic solvent are mutual
It is molten, it is common high boiling point polar (hydrophily) solvent of chemical reaction；N-Methyl pyrrolidone volatility is low, thermal stability, change
It is good to learn stability, most of organic and inorganic compound can be dissolved, be widely applied in lithium electricity industry；Dimethyl acetamide is molten
Agent is a kind of non-proton highly polar solvent, and soluble species range is very wide, can with water, aromatic compound, ester, ketone, alcohol,
Ether, benzene and chloroform etc. are any miscible.The liquid phase medium that the embodiment of the present invention is selected is to polynary small molecule, initiator, monomer
Preferable dissolubility is all had, the components such as polynary small molecule, initiator, monomer in reaction system can be sufficiently dissolved, make reactant
Each component comes into full contact in system, reacts more complete.
In some embodiments, by the polynary small molecule, initiator and monomer in liquid phase medium with 300~500rpm
Mixing speed, stirring and dissolving.
The embodiment of the present invention is not specifically limited the dosage of solvent, as long as being able to satisfy reaction requirement.In some realities
It applies in example, the volume of the liquid phase medium is 1~5 times of the volume of the monomer.
In some embodiments, first polynary small-molecule substance can be dissolved in advance, is avoided because of polynary small molecule object
Matter dissolution not exclusively influences subsequent reactions efficiency and adequacy.
As a preferred embodiment, when the polynary small molecule is small molecule polyol, the item for carrying out polymerization reaction
Part are as follows: under conditions of temperature is 30 DEG C~90 DEG C, it is small to be stirred to react 12 hours~24 with the mixing speed of 300~500rpm
When；When the polynary small molecule is the halides of the small molecule polyol, the condition of the polymerization reaction are as follows: lazy in drying
Property atmosphere under, temperature be 30 DEG C~90 DEG C under conditions of, be stirred to react 12 hours with the mixing speed of 300~500rpm
~24 hours.When the polynary small molecule is the halides of small molecule polyol, the system of polymerization reaction be atom transfer from
(ATRP) is polymerize by base, at this point, the condition of polymerization reaction requires anhydrous and oxygen-free, therefore the condition for carrying out polymerization reaction are as follows:
Under dry inert gas atmosphere, temperature is 30 DEG C~90 DEG C, and mixing speed is 300~500rpm, and mixing time is 12 hours
~24 hours.Dry inert gas atmosphere provides the environment of anhydrous and oxygen-free for reaction system, meets subsequent reactions demand, is conducive to
The progress of reaction.The dry inert gas atmosphere can be by being arranged the drying devices such as drying tube in the reaction system, and is passed through
The inert gases such as nitrogen, argon gas, helium are realized.When the polynary small molecule is small molecule polyol, polymerization reaction system is
Redox free radical system polymerization, at this point, stating the condition for carrying out polymerization reaction are as follows: temperature is 30 DEG C~90 DEG C, mixing speed
For 300~500rpm, mixing time is 12 hours~24 hours.Reaction temperature and time are the key conditions for influencing reaction,
Reaction temperature is too low, is unable to reach polymerization temperature condition, and polymerization reaction can not carry out；Reaction temperature is excessively high, and polymerization reaction is too fast,
Polymerization process is uncontrolled, it is difficult to obtain the non-linear binder of expected highly branched chain arm.Reaction time is too short, polymerization efficiency and
Yield is all very low；Reaction time is too long, and polymerization reaction is completed, and promotes to generate more by-products, while causing unnecessary
The waste of resource and time cost.
As a preferred embodiment, the polynary small molecule and the molar ratio of the monomer are 1:(500~10000).Due to
When binder molecular weight is too low, bonding agent molecule intensity itself is insufficient, and cohesive force is also insufficient, therefore binder needs centainly
Molecular weight provides the intensity and viscosity of binder.And the binder preparation difficulty for crossing high molecular weight is high, bonding viscosity is excessively high
It is unfavorable for the techniques such as stirring, the pole coating of cell size.The embodiment of the present invention, by controlling polynary small molecule and the monomer
Molar ratio be 1:(500~10000), the molecular weight of the binder of formation is controlled, so that there have binder to be suitable strong enough
Degree and viscosity.
As a preferred embodiment, the initiator amount is 1~2 times of reaction site molal quantity in the polynary small molecule
Number.Polynary small molecule provides more polymerization sites for the polymerization of branch chain arm, and the molar ratio of initiator should be according to polynary small molecule
In polymerization reaction number of sites determine.The binder of preparation of the embodiment of the present invention is nonlinear multi-arm binder, therefore, to make
Binder forms linear structure, and polynary small molecule is at least needed there are three polymerization reaction site.In some embodiments, polynary small
Molecule is the ternary small molecule there are three reaction site, and the dosage of initiator is reaction site (three) in ternary small molecule at this time
The molar percentage of 1~2 times of molal quantity, i.e. ternary small molecule and the initiator is 1:(3~6), it can by polymerization reaction
Form the non-linear binder of three chain arms.In further embodiments, polynary small molecule is the quaternary there are four reaction site
Small molecule, the dosage of initiator is 1~2 times of reaction site (four) molal quantity in quaternary small molecule, i.e. small point of quaternary at this time
The sub molar percentage with the initiator is 1:(4~8), the non-linear bonding of four chain arms can be formed by polymerization reaction
Agent.
In some embodiments, the polynary small molecule and the molar ratio of the monomer are 1:(500~10000)；It is described
Initiator amount is 1~2 multiple of reaction site molal quantity in the polynary small molecule.Specifically, in above-mentioned steps S30,
In some embodiments, the monomer is acrylic monomer, and acrylic monomer is selected from acrylic monomers or Acrylates
Monomer, the crude product obtained after polymerization reaction are the non-linear homopolymerization containing polyacrylic acid or polyacrylate branch chain arm
Object, at this time, it is only necessary to the crude product be purified, can be obtained nonlinear lithium ion battery binder.In some embodiments
In, the method for crude product purifying can be extraction, dissolve precipitating repeatedly by the good solvent and poor solvent of crude product, extracts, goes
Except impurity such as by-products, purer crude product is obtained.
In further embodiments, the monomer is non-acrylic monomer, the crude product obtained after polymerization reaction
Practical is containing the intermediate product for corresponding to functional group in monomer, at this point, corresponding to the non-thread of functional group containing non-acrylic monomer
Property homopolymer cannot achieve the adhesive effect of polyacrylic acid branch chain arm homopolymer, need just obtain to after its further conversion processing
Obtain the non-linear lithium ion battery binder containing polyacrylic acid branch chain arm.
In a specific embodiment, when using acrylic ester monomer polymerization, practical obtained crude product is a plurality of poly- third
The intermediate product of enester branch chain arm composition, needs the intermediate product formed to polypropylene ester branch chain arm first to purify, so at this time
The processing of ester decomposition and inversion is carried out afterwards, and last repurity processing obtains the non-linear lithium-ion electric being made of polyacrylic acid branch chain arm
Pond binder.Specifically, the method for ester decomposition and inversion are as follows: a certain amount of intermediate product is dissolved in good solvent, is stirred, then drip
Add the trifluoroacetic acid of corresponding amount, stir certain time, completes ester and decompose, acquisition is made of non-thread a plurality of polyacrylic acid branch chain arm
Property binder.Preferably, the good solvent can be the energy such as methylene chloride, chloroform, n-butanol, ethyl acetate, diethyl ether sufficiently
Dissolve the solvent for the crude product being made of a plurality of polypropylene ester branch chain arm.
In another specific embodiment, when using the polymerization of acrylic acid nitrile monomer, logical obtained crude product is practical to be
The intermediate product of a plurality of polyacrylonitrile branch chain arm composition, needs the intermediate product formed to polyacrylonitrile branch chain arm first to carry out at this time
Purifying, then carries out basic hydrolysis conversion processing, and last repurity processing obtains the non-linear lithium being made of polyacrylic acid branch chain arm
Ion battery binder.Specifically, the method for basic hydrolysis conversion processing are as follows: a certain amount of intermediate product is added to 60 DEG C of 1M hydrogen-oxygen
Change in sodium or lithium hydroxide solution, stir certain time, complete hydrolysis, acquisition is made of non-a plurality of polyacrylate branch chain arm
Linear binder.
In some embodiments, the method for the purifying is extraction, repeatedly molten by the good solvent and poor solvent of crude product
Solution precipitating, extraction, the impurity such as removal by-product obtain purer crude product.
In some embodiments, the method for the repurity are as follows: dialysis.This law inventive embodiments are by by non-linear bonding
Agent reaction mixture is added in bag filter, passes through dialysis, the impurity such as removal small molecule.Obtain pure lithium ion battery binder.
The embodiment of the present invention is not specifically limited molecular cut off, the specification etc. of bag filter, as long as being able to achieve impurity in removal product,
Obtain the effect of pure binder.Specifically, can be divided according to raw material, the pre-synthesis binder of selected synthetic binder
The factors such as the size of son amount, select the molecular cut off of suitable bag filter.In some embodiments, the retention molecule of bag filter
Amount may is that 3500Da, 80000Da, 10000Da, 14000Da etc..
In some embodiments, the method for the purifying is extraction；It is described when the monomer is acrylic acid nitrile monomer
The method of conversion processing is basic hydrolysis；When it is propylene esters monomer that the monomer, which is selected from, the method for the conversion processing is ester
The method of the conversion processing is decomposed as ester decomposition；The method of the repurity is dialysis.
Lithium ion battery binder provided in an embodiment of the present invention is primarily useful in electrodes of lithium-ion batteries, due to containing
It is above-mentioned there are various dimensions efficiently bond, water solubility and non-linear lithium ion battery binder flexible, therefore, the embodiment of the present invention
The electrodes of lithium-ion batteries performance and pole piece structure of offer are stablized, and crackle, peeling etc. are not likely to produce in circulating battery to be caused to follow
The problem of ring performance difference, is able to satisfy the demand of the silicon-based anode lithium ion battery of high-energy density.
The embodiment of the invention also provides a kind of lithium ion battery, the lithium ion battery includes above-mentioned lithium ion battery
Binder；And/or the lithium ion battery includes above-mentioned electrodes of lithium-ion batteries.
Lithium ion battery provided in an embodiment of the present invention, due to containing it is above-mentioned have various dimensions efficiently bond, water solubility and
Non-linear lithium ion battery binder flexible, and/or, the electrodes of lithium-ion batteries containing above-mentioned performance and stable structure, because
This, lithium ion battery provided in an embodiment of the present invention has preferable cyclical stability and safety.
Above-mentioned technical proposal is illustrated below by way of multiple embodiments.
Embodiment 1
S10. by 10mM trimethylolpropane bromo-derivative, PEMTA/CuBr (five methyl diethylentriamine/copper bromide)
(30mM/30mM) initiator and 5M Tert-butyl Methacrylate monomer, under dry inert gas atmosphere, with molten in reaction kettle
Agent DMF obtains lysate with 300~500rpm mixing speed, stirring and dissolving；
S20. by the lysate, under dry inert gas atmosphere, raising reaction temperature is to 80 DEG C, mixing speed
300rpm, reaction for 24 hours, after cooling, obtain crude product；
S30. the crude product is dissolved into deposition and purification with good poor solvent repeatedly；Then multi-arm (3 arm) after purification is poly-
Tert-butyl Methacrylate hydrolyzes under the action of trifluoroacetic acid；Finally product is dialysed, freeze-drying obtains non-linear lithium-ion electric
Pond binder 1, molecular structure is as described in Fig. 1.
Embodiment 2
S10. by 10mM pentaerythrite, 40M ammonium ceric nitrate initiator and 20M acrylonitrile monemer, with 5 times in reaction kettle
The aqueous solvent of monomer volume, with 300~500rpm mixing speed, stirring and dissolving obtains lysate；
S20. by the lysate, reaction temperature is increased to 40 DEG C, mixing speed 300rpm, is reacted for 24 hours, after cooling,
Obtain crude product；
S30. the crude product is dissolved into deposition and purification with good poor solvent repeatedly；Then multi-arm (4 arm) after purification is poly-
Acrylonitrile acts on basic hydrolysis in 1M LiOH；Product dialysis freeze-drying is finally obtained into non-linear lithium ion battery binder 2, molecule
Structure is as shown in Fig. 2.
Embodiment 3
The embodiment of the present invention provides a kind of lithium ion battery.
The non-linear lithium ion battery binder 1 that the embodiment of the present invention 1 is prepared is born with acetylene black conductor and silicon
Pole material is mixed by the mass ratio of 10:20:70, and obtained mixture is applied in copper foil current collector, uses punching after 110 DEG C of drying
Mechanism obtains the electrode slice that diameter is 12mm；
Using obtained electrode slice as cathode, to extremely metal lithium sheet, diaphragm is Celgard 2400, and electrolyte solution is
1mol/L LiPF6Ethylene carbonate, methyl ethyl carbonate (v/v=1:1) mixed solution, Chinese vigor company production it is lazy
Property atmosphere glove box (O2And H2The content of O is respectively less than 0.1ppm) in assembling obtain CR2016 button half-cell 1.
Embodiment 4
The embodiment of the present invention provides a kind of lithium ion battery.
Non-linear lithium ion battery binder 1 that the embodiment of the present invention 1 is prepared and silicon oxygen/graphite composite material by
The mass ratio of 10:5:85 mixes, and obtained mixture is applied in copper foil current collector, is made straight with sheet-punching machine after 110 DEG C of drying
Diameter is the electrode slice of 12mm；
Using obtained electrode slice as cathode, to extremely metal lithium sheet, diaphragm is Celgard 2400, and electrolyte solution is
1mol/L LiPF6Ethylene carbonate, methyl ethyl carbonate (v/v=1:1) mixed solution, Chinese vigor company production it is lazy
Property atmosphere glove box (O2And H2The content of O is respectively less than 0.1ppm) in assembling obtain CR2016 button half-cell 2.
Comparative example 1
This comparative example provides a kind of lithium ion battery.
The binder of this comparative example uses linear polyacrylic acid, presses 10:20:70 with acetylene black conductor and silicium cathode material
Mass ratio mixing, obtained mixture is applied in copper foil current collector, diameter is made with sheet-punching machine is 12mm after 110 DEG C of drying
Electrode slice；
Using obtained electrode slice as cathode, to extremely metal lithium sheet, diaphragm is Celgard 2400, and electrolyte solution is
1mol/L LiPF6Ethylene carbonate, methyl ethyl carbonate (v/v=1:1) mixed solution, Chinese vigor company production it is lazy
Property atmosphere glove box (O2And H2The content of O is respectively less than 0.1ppm) in assembling obtain CR2016 button half-cell comparative example 1.
Comparative example 2
This comparative example provides a kind of lithium ion battery.
The binder of this comparative example uses linear polyacrylic acid, presses with acetylene black conductor and silicon oxygen/graphite composite material
The mass ratio of 10:5:85 mixes, and obtained mixture is applied in copper foil current collector, is made straight with sheet-punching machine after 110 DEG C of drying
Diameter is the electrode slice of 12mm；
Using obtained electrode slice as cathode, to extremely metal lithium sheet, diaphragm is Celgard 2400, and electrolyte solution is
1mol/L LiPF6Ethylene carbonate, methyl ethyl carbonate (v/v=1:1) mixed solution, Chinese vigor company production it is lazy
Property atmosphere glove box (O2And H2The content of O is respectively less than 0.1ppm) in assembling obtain CR2016 button half-cell comparative example 2.
Performance test
1, nuclear magnetic resonance
The non-linear lithium ion that the present invention uses 400 nuclear magnetic resonance of broker (NMR) to provide the embodiment of the present invention 1 and 2
The characterization that battery binder 1 and 2 is formed, as shown in figures 3 and 4.
As shown in Fig. 3, the non-linear lithium ion battery binder 1 prepared for the embodiment of the present invention 1, hydrolysis front and back are (poly-
Polymethyl ester after conjunction and the multi-arm of hydrolysis (3 arm) polyacrylic acid) compound characteristic peak hydrogen nuclear magnetic resonance spectrogram.Through
The characteristic peak of multi-arm (3 arm) polyacrylic acid of NMR detection, the polymethyl ester after polymerization and hydrolysis is detected, it was demonstrated that
The successful progress of reaction.Specifically, before hydrolysis ,-CH in multi-arm tert-butyl acrylate2H (a) and the tert-butyl ester on-CH3(c)
Corresponding H spectrum signature peak is in 1.1-1.7ppm, and the characteristic peak of-CH- (b) is in 2.0-2.5ppm, the integral area ratio at two groups of peaks
Also it coincide with its stoichiometric ratio.After hydrolysis (ester decomposition), the H characteristic peak on ter-butyl ester groups disappears, acrylic acid units-
CH2On hydrogen (a) and-CH- on hydrogen (b) characteristic peak respectively appear in 2.2-2.7ppm and 1.3-2.1ppm goes out, peak area
Than also coincideing with its stoichiometric ratio.
As shown in Fig. 4, the non-linear lithium ion battery binder 2 prepared for the embodiment of the present invention 2, hydrolysis front and back are (more
Arm (4 arm) polyacrylonitrile and multi-arm (4 arm) Lithium polyacrylate) compound characteristic peak hydrogen nuclear magnetic resonance spectrogram.It is examined through NMR
It surveys, the characteristic peak of multi-arm (4 arm) polyacrylonitrile and multi-arm (4 arm) Lithium polyacrylate is detected, it was demonstrated that the success of reaction
It carries out.Specifically, before hydrolysis, multi-arm polyacrylonitrile-CH2H (a) and the tert-butyl ester on-CH3(c) corresponding H spectrum signature peak exists
1.8-2.3ppm, and the characteristic peak of-CH- (b) is in 3.0-3.3ppm, the integral area ratio at two groups of peaks is also kissed with its stoichiometric ratio
It closes.After hydrolysis (caustic digestion), the H characteristic peak near CN disappears, and-the CH of acrylic acid units occurs2On hydrogen (a) and-CH- on
Hydrogen (b) characteristic peak respectively appear in 0.9-1.7ppm and 1.8-2.5ppm goes out, peak area ratio is also kissed with its stoichiometric ratio
It closes.
2, performance of lithium ion battery is tested
The present invention combines obtained binder to obtain lithium ion battery, by electrochemistry loop test, investigates different viscous
Tie the chemical property of the lithium ion battery of agent.Specifically, using the electricity of the model CT 2001A of Wuhan Lan electricity company production
Pond test macro, to CR216 button half-cell 1 provided in an embodiment of the present invention, CR216 button half-cell 2 and CR216 button half
Battery comparative example 1 tests the cyclical stability of lithium ion battery, the voltage range of test condition by electrochemistry loop test
For 0.01~1.0V and 0.01-2.0V, cycle period 200.
The result shows that as shown in Fig. 5, the non-linear lithium ion battery binder system provided using the embodiment of the present invention 3
At silicium cathode battery 1, under room temperature, the electric current of 840mA/g, specific discharge capacity still can reach 2100mAh/g after 200 weeks,
And battery 1 provided in an embodiment of the present invention has preferable cyclical stability, specific capacity maintains always more stable in cyclic process
State show superior cycle performance basically no attenuation.And the battery comparative example 1 that comparative example 1 provides, in 200 Zhou Houfang
Electric specific capacity is significantly lower than the battery 1 that the embodiment of the present invention 3 provides, and is always in downward trend.
As shown in Fig. 6, silicon oxygen made of the non-linear lithium ion battery binder provided using the embodiment of the present invention 4/
Graphite composite negative pole battery 2, under room temperature, the electric current of 160mA/g, first specific discharge capacity 600mAh/g, discharge specific volume after 200 weeks
Amount still can maintain 590mAh/g, be demonstrated by superior cycle performance, attenuation rate is small.And the battery comparison that comparative example 2 provides
Example 2, puts specific capacitance for the first time and specific discharge capacity is significantly lower than the battery 2 of the offer of the embodiment of the present invention 4 after 200 weeks, and declines
It is obvious to subtract trend.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of preparation method of lithium ion battery binder, which comprises the following steps:
Polynary small molecule, initiator and monomer are obtained, the monomer is selected from acrylic monomer or non-acrylic monomer；
By the polynary small molecule, initiator and the monomer mixed dissolution in liquid phase medium, polymerization reaction is carried out, obtains thick produce
Object；
When the monomer is acrylic monomer, the crude product is purified, nonlinear lithium ion battery binder is obtained；
When the monomer is non-acrylic monomer, after purification by the crude product, conversion processing is carried out, is purified again, obtained non-
Linear lithium ion battery binder.
2. the preparation method of lithium ion battery binder as described in claim 1, which is characterized in that the polynary small molecule choosing
From: the halides of small molecule polyol or small molecule polyol, the small molecule polyol are at least containing there are three hydroxyls
Small molecule polyol.
3. the preparation method of lithium ion battery binder as described in claim 1, which is characterized in that the acrylic monomer
Selected from acrylic monomers or Acrylates monomer；And/or
The non-acrylic monomer is selected from acrylic ester monomer or acrylonitrile monomer.
4. the preparation method of lithium ion battery binder as described in claim 1, which is characterized in that when the polynary small molecule
When for small molecule polyol, the initiator is selected from: potassium peroxydisulfate, ammonium persulfate, ammonium ceric nitrate, anhydrous calcium chloride, hydrogen peroxide
At least one of；
When the polynary small molecule is the halides of small molecule polyol, the initiator is selected from: pentamethyl diethylidene three
Amine/copper bromide, tetramethylethylenediamine/copper bromide, hexamethyl trien/copper bromide, three (N, N- dimethylaminoethyls
Base) amine/copper bromide, five methyl diethylentriamine/copper chloride, tetramethylethylenediamine/copper chloride, hexamethyl triethylene four
At least one of amine/copper chloride, three (N, N- dimethyl aminoethyl) amine/copper chlorides.
5. the preparation method of lithium ion battery binder as claimed in claim 2, which is characterized in that when the polynary small molecule
When for small molecule polyol, the liquid phase medium is selected from: n,N-Dimethylformamide, N-Methyl pyrrolidone, N, N- dimethyl
It is one or more of in acetamide or aqueous solvent；
When the polynary small molecule is the halides of small molecule polyol, the liquid phase medium is selected from: N, N- dimethyl formyl
It is one or more of in amine, N-Methyl pyrrolidone or DMAC N,N' dimethyl acetamide.
6. the preparation method of lithium ion battery binder as claimed in any one of claims 1 to 5, wherein, which is characterized in that described
Polynary small molecule and the molar ratio of the monomer are 1:(500~10000)；And/or
The initiator amount is 1~2 multiple of reaction site molal quantity in the polynary small molecule.
7. the preparation method of the lithium ion battery binder as described in claim 2~5 any one, which is characterized in that work as institute
State polynary small molecule be small molecule polyol when, the condition of the polymerization reaction are as follows: temperature be 30 DEG C~90 DEG C under conditions of,
It is stirred to react 12 hours~24 hours with the mixing speed of 300~500rpm；
When the polynary small molecule is the halides of small molecule polyol, the condition of the polymerization reaction are as follows: in dry inertia
Under atmosphere, temperature be 30 DEG C~90 DEG C under conditions of, with the mixing speed of 300~500rpm be stirred to react 12 hours~
24 hours.
8. the preparation method of lithium ion battery binder as described in claim 1, which is characterized in that the method for the purifying is
Extraction；And/or
When the monomer is acrylic acid nitrile monomer, the method for the conversion processing is basic hydrolysis；When the monomer is propylene
When esters monomer, the method for the conversion processing is ester decomposition；And/or
The method of the repurity is dialysis.
9. a kind of lithium ion battery binder, which is characterized in that the lithium ion battery binder includes by polynary small molecule
The non-linear multi-arm of parent nucleus and the polyacrylic acid being connected on the polynary small molecule parent nucleus or polyacrylate branch chain arm composition
Homopolymer.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery includes lithium ion as claimed in claim 9
Battery binder.
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