CN106700013A - Strong polar polymer adhesive as well as synthesis method and application thereof in lithium battery - Google Patents
Strong polar polymer adhesive as well as synthesis method and application thereof in lithium battery Download PDFInfo
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- CN106700013A CN106700013A CN201610971296.0A CN201610971296A CN106700013A CN 106700013 A CN106700013 A CN 106700013A CN 201610971296 A CN201610971296 A CN 201610971296A CN 106700013 A CN106700013 A CN 106700013A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3806—Polyhydroxy compounds having chlorine and/or bromine atoms
- C08G18/3808—Polyhydroxy compounds having chlorine and/or bromine atoms having chlorine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
- C08G18/3804—Polyhydroxy compounds
- C08G18/3812—Polyhydroxy compounds having fluorine atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/3838—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing cyano groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
- C08G18/384—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen containing nitro groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/6423—Polyalkylene polyamines; polyethylenimines; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6484—Polysaccharides and derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- 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
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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
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- 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 invention provides a strong polar polymer adhesive as well as a synthesis method and application thereof in a lithium battery. A general expression of the chemical structure of the strong polar polymer adhesive is as shown in the specification. The strong polar polymer adhesive has the characteristics of relatively strong polarity and high adhesion property, also has strong electrochemistry polarity, and is capable of adsorbing polar polysulfide generated during a recycling process of a lithium-sulphur battery; the battery using a pole piece prepared by use of the adhesive has the characteristics of excellent recycling performance and high coulomb efficiency; the adhesive is environmentally friendly and has favorable adhesion property on various positive-electrode active substances of the lithium-sulphur battery. Experiments show that after the lithium-sulphur battery using the adhesive is recycled for 200 times under a current density of 0.5c, the capacity retention ratio is as high as 91%.
Description
Technical field
The invention belongs to polymeric material field, it is related to a kind of polymeric binder, and in particular to a kind of highly polar polymerization
Thing binding agent, synthetic method and its application in energy device electrode, the especially application in electrode of lithium cell.
Background technology
With flourishing for modern science and technology, to the concern more and more higher of electronic consumer markets, consumer is to frivolous for people
The use of the mobile electronic devices such as type electronic product mobile phone, panel computer is more and more frequent so that these electronic products
Power consumption is continuously increased；Particularly in recent years, energy of the development of the electric vehicle such as electric automobile also to lithium ion battery is close
Degree proposes requirement higher.And traditional lithium ion battery difficulty has been greatly improved in terms of energy density, at this
In the case of kind, the lithium-sulfur cell with theoretical capacity high and high-energy-density causes the extensive concern of people.
Lithium-sulfur cell generally with elemental sulfur or sulfenyl composite as positive electrode active materials, be dissolved with the ether solvent of lithium salts
It is electrolyte, lithium metal as negative material, its theoretical energy density is 2600Whkg-1, is that a kind of energy density is high, ring
The friendly and cheap secondary cell in border, it is considered to be the important development direction of following power source, with very wide
Application prospect and commercial value.Although lithium-sulfur cell all has very big advantage in many aspects, it is also in charge and discharge cycles
During expose many shortcomings：First, the electric conductivity of sulphur simple substance and electric discharge final product lithium sulfide is all very poor, greatly influences
The derivation of electronics；Secondly, the intermediate product of circulation is soluble in the polysulfide of electrolyte, can be as electrolyte is in both positive and negative polarity
Between shift, result in lithium-sulfur cell sulphur utilization rate is low and the problems such as cyclical stability difference；Meanwhile, sulphur is in charge and discharge process
Volumetric expansion can cause that active material easily comes off from collector, destroy the physical arrangement of electrode.These problems are all tight
The chemical property of conventional lithium-sulfur cell is constrained again, causes electrochemical stability difference and the low shortcoming of capability retention, it is difficult to
Meet the demand of commercial applications.
At present, the sulphur of nano-scale being uniformly distributed in the porous material of good conductivity can preferably keep positive pole
The stability and electric conductivity of structure, the instability problem of the relatively effective electric conductivity and battery structure for solving sulphur；But
The dissolution problem of intermediate product has to be solved.In fact, because there is polarity in the polysulfide in cyclic process, it is possible to
In the preparation process of electrode, polarity absorption polysulfide is reached in electrode surface by adding polar substances on electrode material
Form, so as to reduce because polysulfide is to the effect that shuttled caused by the diffusion in electrolyte.
On the other hand, battery material binding agent is offer active material, conductive additive and collection in electrode production process
The essential additive of the bonding force between fluid, can make lithium ion battery in charge and discharge process holding electrode it is steady
Qualitative and integrality, so binding agent has very important influence to lithium ion battery chemical property.Existing lithium sulphur electricity
Most of binding agent that pond uses be PVDF, but it is big for lithium sulfur battery anode material surface area and porous the characteristics of, PVDF glue
Active material comes off during knot agent can cause pole piece to prepare journey, causes sulphur active material utilization low, Cycle Difference.Meanwhile, generally anticipate
Battery binding agent under justice can not play good restriction effect to polysulfide, and lithium-sulfur cell still has cycle performance difference
Problem.
The content of the invention
A kind of highly polar polymeric binder is provided the invention aims to overcome the deficiencies in the prior art.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of highly polar polymeric binder, its chemistry
General structure is：
The R2And R3Contain independently of each other
There is at least one polar group.
Optimally, the R1It is aromatic radical, alkyl, aralkyl or cycloalkyl.
Optimally, the polar group is selected from-NH2、-OH、-SO3H、-NO2,-CN ,-F ,-Cl, in-Br and-I one
Plant or various.
Optimally, its weight average molecular weight is 1 × 104~2.0 × 105。
A further object of the present invention is to provide a kind of preparation method of above-mentioned highly polar polymeric binder, by that will lead to
Formula is O=C=N-R1The isocyanate compound of-N=C=O is H with formula2N-R2-NH2Aminated compounds or formula be
HO-R3The alcohol compound of-OH carries out polymerisation.
Optimally, the isocyanate compound be selected from 1,3- phenylene diisocyanates, 4,4 '-biphenyl diisocyanate,
1,4- phenylene diisocyanates, 4,4 '-methyl diphenylene diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene diisocyanates
Acid esters, 4,4 '-toluidine diisocyanate, 2,4,6- triisocyanates toluene, 1,3,5- triisocyanates benzene, dianisidine two
Isocyanates, 4,4 '-diphenyl ether diisocyanate, XDI, trimethylene diisocyanate, four Asias
Methyl diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2- trimethylene diisocyanates, 2,
3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, ten dimethylene diisocyanates, 2,4,4- trimethyls six are sub-
Methyl diisocyanate, ω, ω '-diisocyanate -1,3- dimethyl benzenes, ω, ω '-diisocyanate -1,4- dimethyl benzenes,
ω, ω '-diisocyanate -1,4- diethylbenzene, 1,4- tetramethylxylylene diisocyanates, 1,3- durols two be sub-
Methyl diisocyanate, 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanates, the isocyanic acid of 1,4- pentamethylene two
Ester, methyl -2,4- pentamethylene diisocyanate, methyl -2,6- pentamethylene diisocyanate, 4,4 '-methylene bis cyclohexyl are different
Cyanate, one or more mixture of composition in Isosorbide-5-Nitrae-bis- isocyanato methylcyclohexanes.
Optimally, the aminated compounds is It is above-mentioned
In chemical formula：R4It is hydrogen, or includes the chain or cyclic group of at least one carbon atom.
Optimally, the alcohol compound is
Optimally, the preparation method of above-mentioned highly polar polymeric binder, comprises the following steps：A () is by the isocyanic acid
Ester compounds are dissolved in solvent, and heating makes its isonitrile acid groups that scission of link to occur；B () is by the aminated compounds or the alcohols
Compound is dissolved in solvent, is then added thereto to product and initiator (such as cellulose material) that step (a) is obtained, is risen
Temperature reaction is to sticky.
Further, it is transferred to closed brown sample bottle after also including the product cooling that (c) obtains step (b),
Preserve under agitation.
A further object of the present invention is to provide a kind of above-mentioned highly polar polymeric binder as binding agent in energy device
Application in part electrode.
The energy device electrode is lithium-sulphur cell positive electrode, it is preferable that above-mentioned application is comprised the following steps：
(1) to solvent is added in the mixture of positive electrode active materials and conductive agent, added under conditions of being stirred continuously and used
The scattered highly polar polymeric binder of solvent, anode sizing agent is formed after stirring evenly；The positive electrode active materials are branch
The mixture of support carbon material and sulphur powder；(2) anode sizing agent is coated in aluminum foil current collector, is dried.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The present invention is highly polar poly-
The characteristics of compound binding agent has more highly polar, high-adhesion, while in the presence of very strong electrochemistry polarity, can adsorb and result from
The polysulfide of the polarity in lithium-sulfur cell cyclic process, the battery of the pole piece prepared using the binding agent has cycle performance excellent
The characteristics of different and coulombic efficiency is high；The multiple anode active substances of lithium-sulfur cell are had good by the binding agent environmental protection
Caking property.Experiment shows, uses capability retention of the lithium-sulfur cell of the binding agent under the 0.5C current densities after circulation 200 times
Reach as high as 91%.
Brief description of the drawings
Accompanying drawing 1 is the nuclear magnetic spectrogram of polymeric binder in embodiment 1；
Accompanying drawing 2 is the lithium-sulfur cell made of polymeric binder in embodiment 1 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure；
Accompanying drawing 3 is the lithium-sulfur cell made of polymeric binder in embodiment 2 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure；
Accompanying drawing 4 is the lithium-sulfur cell made of polymeric binder in embodiment 3 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure；
Accompanying drawing 5 is the lithium-sulfur cell made of polymeric binder in embodiment 4 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure；
Accompanying drawing 6 is the lithium-sulfur cell made of polymeric binder in embodiment 5 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure；
Accompanying drawing 7 is the lithium-sulfur cell made of polymeric binder in embodiment 6 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure.
Accompanying drawing 8 is the lithium-sulfur cell made of polymeric binder in embodiment 7 and the lithium made using existing binding agent
Sulphur battery electrochemical test comparison figure.
Specific embodiment
The highly polar polymeric binder of the present invention, its chemical structure of general formula is： The R2And R3Contain at least one polar group independently of each other；So so that the polymerization
The characteristics of thing binding agent has more highly polar, high-adhesion, while in the presence of very strong electrochemistry polarity, can adsorb and result from lithium
The polysulfide of the polarity during sulphur circulating battery, the battery of the pole piece prepared using the binding agent has cycle performance excellent
The characteristics of high with coulombic efficiency.
The preparation method of above-mentioned highly polar polymeric binder：It is O=C=N-R by by formula1- N=C=O's is different
Cyanate esters are H with formula2N-R2-NH2Aminated compounds or formula be HO-R3The alcohol compound of-OH is gathered
Close reaction so that the active hydrogen that amino (aminated compounds) or hydroxyl (alcohol compound) contain is connected to isocyanates
On the N atoms of compound isocyanate group, and the other parts of aminated compounds or alcohol compound are connected to isocyanate compound
High molecular polymer is formed on the C atoms of isocyanate group.
In above-mentioned formula, R1Can be chosen from existing group, such as aromatic radical, alkyl, aralkyl or cycloalkyl.Alkyl
In include 3~12 carbon atoms (can be side chain or the alkyl with side chain), such as trimethylene, tetramethylene, five methylenes
The groups such as base, hexa-methylene, 1,2- propylidene, 2,3- butylidenes, ten dimethylenes, 2,4,4- tri-methyl hexamethylenes；Fragrance
Base is includedDeng；Aralkyl is includedDeng；I.e. formula is O=C=N-R1The isocyanate compound of-N=C=O may be selected from fragrance
Race's polyisocyanates (for example 1,3- phenylene diisocyanates, 4,4 '-biphenyl diisocyanate, 1,4- phenylene diisocyanates, 4,4 '-
Methyl diphenylene diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, the isocyanide of 4,4 '-toluidines two
Acid esters, 2,4,6- triisocyanates toluene, 1,3,5- triisocyanates benzene, dianisidine diisocyanate, 4,4 '-diphenyl ether
Diisocyanate, XDI etc.), aliphatic polyisocyante (such as trimethylene diisocyanate, four
Methylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2- trimethylene diisocyanates,
2,3- tetramethylene diisocyanates, 1,3- tetramethylene diisocyanates, ten dimethylene diisocyanates, 2,4,4- trimethyls six
Methylene diisocyanate etc.), aromatic-aliphatic polyisocyanates (such as ω, ω '-diisocyanate -1,3- dimethyl benzenes,
ω, ω '-diisocyanate -1,4- dimethyl benzenes, ω, ω '-diisocyanate -1,4- diethylbenzene, 1,4- durols two are sub-
Methyl diisocyanate, 1,3- tetramethylxylylene diisocyanates, (the 2,6- diethyl phenyl isocyanides of 4,4- methylene two
Acid esters) etc.) and alicyclic polyisocyanates (such as 1,3- pentamethylene diisocyanate, 1,3- cyclohexane diisocyanates, 1,4-
Pentamethylene diisocyanate, methyl -2,4- pentamethylene diisocyanate, methyl -2,6- pentamethylene diisocyanate, 4,4 '-Asia
Methyl bicycle hexyl isocyanates, Isosorbide-5-Nitrae-bis- isocyanato methylcyclohexanes etc.) in one or more composition mixture.
And R2And R3In it is separate containing at least one polar group be selected from-NH2、-OH、-SO3H、-NO2、-CN、-
One or more in F ,-Cl ,-Br and-I.R2And R3The fragrance containing at least one polar group can be independently of one another
Base, alkyl, aralkyl or cycloalkyl, such H2N-R2-NH2Aminated compounds can be Deng conventional material, (m is 1~10 integer, R5
It is polar group, it can be obtained by carrying out substitution reaction on diamine compounds), or Etc. complex material, R4For hydrogen or include at least one
The chain or cyclic group of individual carbon atom.Formula is HO-R3The alcohol compound of-OH may be referred to above-mentioned conventional aminated compounds
Structural formula, or Etc. complex material.
The weight average molecular weight of the highly polar polymeric binder can be selected according to actual needs, or according to above-mentioned
Reaction time length, reaction temperature of reaction etc. are adjusted.The highly polar polymeric binder is typically dispersed in organic molten
Emulsion is formed in agent and use (similar to existing PVDF emulsions), as long as therefore can be dispersed in organic solvent and form equal
One emulsion simultaneously can finally be bonded to electrode material；The weight average molecular weight of the highly polar polymeric binder is preferably
1×104~2.0 × 105。
Preferably, the preparation method of above-mentioned highly polar polymeric binder, comprises the following steps：A () is by the isocyanic acid
Ester compounds are dissolved in solvent, and heating makes its isonitrile acid groups that scission of link to occur；B () is by the aminated compounds or the alcohols
Compound is dissolved in solvent, is then added thereto to product and initiator (such as cellulose material) that step (a) is obtained, is risen
Temperature reaction (typically 90~150 DEG C) is extremely sticky.The solvent is dimethylacetylamide (DMAc), N,N-dimethylformamide
Etc. (DMF) organic solvent of above-mentioned reactant, preferably DMF can be dissolved.In order to improve each monomer dispersiveness in a solvent,
Appropriate dispersant can be added to dispersion, the addition amount and type of dispersant have no special requirements, it is intended to can improve monomer
Dispersiveness and the polymer of subsequent polymerisation or formation will not be had adverse effect on；In order to improve monomer dispersion
The stability of liquid, can in right amount add stabilizer (stabilizer is epoxides), and addition is not particularly limited, can stable dispersions
.It is transferred to closed brown sample bottle after also including the product cooling that (c) obtains step (b), under agitation
Preserve.
A further object of the present invention is to provide a kind of above-mentioned highly polar polymeric binder as binding agent in energy device
Application in part electrode.The energy device electrode is lithium-sulphur cell positive electrode, it is preferable that above-mentioned application is comprised the following steps：(1)
Solvent is added in mixture to positive electrode active materials and conductive agent (such as acetylene black, Ketjen black, ultra-fine carbon dust, electrically conductive graphite)
(dimethylacetylamide (DMAc), DMF (DMF) equal solvent), adds described under conditions of being stirred continuously
The scattered highly polar polymeric binder of solvent, anode sizing agent is formed after stirring evenly；The positive electrode active materials are support carbon
Material (such as carbonaceous mesophase spherules MCMB, Delanium or multi-walled carbon nano-tubes MWCNT any one carbon material) is mixed with sulphur powder
Compound；(2) anode sizing agent is coated in aluminum foil current collector, is dried.Above-mentioned highly polar polymeric binder is in electricity
Percentage by weight in pole material (being the gross mass of active material, conductive agent and binding agent) is 5~20%.In step (1), will
Positive active material and conductive agent are added in organic solvent, stir 0.5~2 with the speed of 1000~2000r/min at room temperature
After hour, binding agent is added, then the anode sizing agent prepared after being stirred 2 hours with the speed of 500~2000r/min.Step
Suddenly in (2), the slurry is spread evenly across on collector (such as aluminium foil, Copper Foil, nickel foam), after being dried at 50~80 DEG C
(5~24 hours), are cut into the pole piece of certain size (such as), (5~24 is small for drying under 70~100 DEG C of vacuum environments
When).
The present invention is further described below in conjunction with accompanying drawing embodiment.
Embodiment 1
The present embodiment provides a kind of highly polar polymeric binder, it by
(HDI, hexamethylene diisocyanate) and macromolecule(PEI, Aladdin reagent,
CAS：25987-06-8) hydro-thermal polymerization at high temperature；
Specific implementation step is as follows：
A () takes the HDI monomers of 5g, be well-dispersed in 40ml DMF, and adds 0.1g oxirane as stabilizer, plus
Heat is reacted 1 hour so that the C=N scission of links on HDI monomers to 120 DEG C of condensing refluxes；
B () will be dispersed with the 40ml DMF solutions of 5g PEI immigration 100ml reactors, and immediately in addition step (a)
Above-mentioned solution；0.1g celluloses are added, is well mixed, be heated to 120 DEG C of pyroreactions 2 hours；
C () is down to room temperature, be transferred in 100ml brown sample bottles, and after sealing, not well-proportioned speed stirring is preserved；Gained is polymerized
Thing binding agent is in milky white mucus；By gel permeation chromatography (GPC), the weight average molecular weight for measuring polymer molecule is about
41000。
Fig. 1 is the polymeric binder nuclear magnetic spectrogram of synthesis, the resonance signal at δ=163.58ppm and 159.45ppm
Respectively N-CH=O and N=C-OH, shows that amino and NCO are polymerized.
Embodiment 2
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：It by HDI monomers and(C6H8O3N2S) hydro-thermal polymerization, resulting polymers at high temperature
Binding agent is in faint yellow mucus.By gel permeation chromatography (GPC), the weight average molecular weight about 87000 of polymer molecule is measured.
Embodiment 3
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：It by HDI monomers and(C6H7N3O2) hydro-thermal polymerization at high temperature；Resulting polymers
Binding agent gray mucus.By gel permeation chromatography (GPC), the weight average molecular weight for measuring polymer molecule is about 73000.
Embodiment 4
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：It by HDI monomers and(C4N4H4) hydro-thermal polymerization at high temperature；Resulting polymers binding agent is in
Grey mucus.By gel permeation chromatography (GPC), the weight average molecular weight for measuring polymer molecule is about 57000.
Embodiment 5
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：It by HDI monomers and(C10H6F16O2) at high temperature hydro-thermal gather
Close；Resulting polymers binding agent is in yellowish mucus.By gel permeation chromatography (GPC), dividing equally again for polymer molecule is measured
Son amount about 13000.
Embodiment 6
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：It by HDI monomers and(C2H3O2Cl3) at high temperature hydro-thermal be polymerized；Resulting polymers
Binding agent is in milky white mucus.By gel permeation chromatography (GPC), the weight average molecular weight for measuring polymer molecule is about 26000.
Embodiment 7
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：It by HDI monomers and(amylopectin) hydro-thermal is gathered at high temperature
Conjunction is formed；Resulting polymers binding agent is in milky white mucus.By gel permeation chromatography (GPC), the weight of polymer molecule is measured
Average molecular weight is about 132000.
Embodiment 8
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, unlike：By trimethylene diisocyanate and PEI molecules, hydro-thermal is polymerized at high temperature for it.
Embodiment 9
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is tetramethylene diisocyanate.
Embodiment 10
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is ten dimethylene diisocyanates.
Embodiment 11
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is 2,3- tetramethylene diisocyanates.
Embodiment 12
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is 1,3- phenylene diisocyanates.
Embodiment 13
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is 4,4 '-biphenyl diisocyanate.
Embodiment 14
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is ω, ω '-diisocyanate -1,3- dimethyl benzenes.
Embodiment 15
The embodiment of the present invention provides a kind of highly polar polymeric binder, in its preparation method and embodiment 1 basic one
Cause, the difference is that its reaction raw materials is 1,3- pentamethylene diisocyanate.
Experimental example 1
The polymer synthesized in embodiment 1 to embodiment 15 is made into corresponding lithium-sulphur cell positive electrode as binding agent respectively
And lithium-sulfur cell, specific implementation step is as follows：
(1) by ball-milled mixtures (wherein, the matter of MCBC and sulphur powder of the carbonaceous mesophase spherules (MCBC) of 7g and business sulphur powder
Amount is than being 3:7) added with the acetylene black of 2g in the DMF of 0.1ml, stirred 1 hour with the speed of 1500r/min at room temperature；With
Binding agent, existing PVDF binding agents in the embodiment 1 of 1g to embodiment 15 are separately added into afterwards, then with the speed of 1000r/min
The slurry that degree stirring is prepared after 2 hours (is obtained the 15 parts of samples and PVDF corresponding to embodiment 1 to embodiment 15
Control sample, adds up to 16 parts of samples)；
(2) slurry is spread evenly across on aluminium foil, after being dried 12 hours at 60 DEG C, is cut into the pole piece of φ 12mm,
Dried 12 hours under 80 DEG C of vacuum environments；
(3) positive pole, lithium anode, barrier film (celgard 2400) and the electrolyte that will be prepared (contain 1mol/
The DOL (1,3 dioxolanes) of the LiTFSI of L and DME (glycol dimethyl ether) mixed solution, the volume ratio of DOL and DME is 1:1)
Button cell (totally 20 batteries, corresponding to 20 parts in step (1) are assembled into argon gas glove box of the water content less than 1ppm
Sample).
The constant current charge-discharge that 15 batteries obtained above are carried out at room temperature on Land cell testers is tested, is cut
Only voltage is 1.5~3.0V, and test electric current is 0.5C (837mA/g), and cycle-index is 200 times, and its cycle performance figure is right respectively
Answer Fig. 2~Fig. 7.From Fig. 2~Fig. 7, the new polymers binding agent prepared using the method for the invention may be such that lithium sulphur
The cycle performance of battery is greatly improved, capacity of the corresponding lithium-sulfur cell under the 0.5C current densities after circulation 200 times
Conservation rate is listed in the table, is above the capability retention of comparative example lithium-sulfur cell (PVDF binding agents) 49%, shows this hair
Performance of the bright binding agent in terms of lithium-sulfur cell cycle performance is improved is protruded very much, and specific data are shown in Table 1.
In the embodiment 1 of table 1 to embodiment 15 synthesize polymer as the lithium-sulfur cell of binding agent test data
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (12)
1. a kind of highly polar polymeric binder, it is characterised in that its chemical structure of general formula is：
Or；The R2And R3Independently of each other containing extremely
A few polar group.
2. highly polar polymeric binder according to claim 1, it is characterised in that：The polar group be selected from-
NH2、-OH、-SO3H、-NO2,-CN ,-F ,-Cl, one or more in-Br and-I.
3. highly polar polymeric binder according to claim 1, it is characterised in that：The R1It is aromatic radical, alkyl, virtue
Alkyl or cycloalkyl.
4. highly polar polymeric binder according to claim 1, it is characterised in that：Its weight average molecular weight is 1 × 104~
2.0×105。
5. in Claims 1-4 any highly polar polymeric binder preparation method, it is characterised in that：It is by formulaIsocyanate compound be with formulaAminated compounds or formula beAlcohol compound carry out polymerisation.
6. the preparation method of highly polar polymeric binder according to claim 5, it is characterised in that：The isocyanation esterification
Compound is selected from 1,3- phenylene diisocyanates, 4,4 '-biphenyl diisocyanate, 1,4- phenylene diisocyanates, 4,4 '-diphenylmethyl
Alkane diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI)s, 4,4 '-toluidine diisocyanate, 2,4,
6- triisocyanates toluene, 1,3,5- triisocyanates benzene, dianisidine diisocyanate, the isocyanic acid of 4,4 '-diphenyl ether two
Ester, XDI, trimethylene diisocyanate, tetramethylene diisocyanate, the isocyanide of pentamethylene two
Acid esters, hexamethylene diisocyanate, 1,2- trimethylene diisocyanates, 2,3- tetramethylene diisocyanates, 1,3- butylidenes
Diisocyanate, ten dimethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanates, ω, the isocyanides of ω '-two
Acid esters -1,3- dimethyl benzenes, ω, ω '-diisocyanate -1,4- dimethyl benzenes, ω, ω '-diisocyanate -1,4- diethyls
Benzene, 1,4- tetramethylxylylene diisocyanates, 1,3- tetramethylxylylene diisocyanates, 1,3- pentamethylene two
Isocyanates, 1,3- cyclohexane diisocyanates, 1,4- pentamethylene diisocyanate, methyl -2,4- pentamethylene diisocyanate,
The double isocyanatomethyl hexamethylenes of methyl -2,6- pentamethylene diisocyanate, 4,4 '-methylene bis cyclohexyl isocyanates and 1,4-
One or more mixture of composition in alkane.
7. the preparation method of highly polar polymeric binder according to claim 5, it is characterised in that：The aminated compounds
For、、、
、、、、、、、Or；R4Be hydrogen, or include at least one carbon atom chain or
Cyclic group.
8. the preparation method of highly polar polymeric binder according to claim 5, it is characterised in that：The alcohol compound
For、、、、、、、、、Or。
9. the preparation method of highly polar polymeric binder according to claim 5, it is characterised in that it includes following step
Suddenly：
（a）The isocyanate compound is dissolved in solvent, heating makes its isonitrile acid groups that scission of link to occur；
（b）The aminated compounds or the alcohol compound are dissolved in solvent, step is then added thereto to（a）Obtain
Product and initiator, temperature reaction is to sticky.
10. the preparation method of highly polar polymeric binder according to claim 9, it is characterised in that it also includes：
（c）By step（b）Closed brown sample bottle is transferred to after the product cooling for obtaining, is preserved under agitation.
In 11. Claims 1-4 any highly polar polymeric binder as binding agent in energy device electrode should
With.
12. according to claim 11 highly polar polymeric binder application, the energy device electrode be lithium-sulfur cell
Positive pole, it is characterised in that it is comprised the following steps：
（1）Solvent is added in mixture to positive electrode active materials and conductive agent, is added described under conditions of being stirred continuously
The scattered highly polar polymeric binder of solvent, anode sizing agent is formed after stirring evenly；The positive electrode active materials are support carbon
The mixture of material and sulphur powder；
（2）The anode sizing agent is coated in aluminum foil current collector, is dried.
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| PCT/CN2016/113017 WO2018082181A1 (en) | 2016-11-07 | 2016-12-29 | Strong polar polymer adhesive, synthetic method, and application thereof in lithium battery |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107863534A (en) * | 2017-10-20 | 2018-03-30 | 电子科技大学 | A kind of polarity bonding agent applied to lithium-sulfur cell and preparation method thereof |
| CN110144033A (en) * | 2019-04-25 | 2019-08-20 | 合肥国轩高科动力能源有限公司 | The preparation method of waterborne polyurethane binders and lithium ion battery anode glue size including the binder |
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| CN112011026A (en) * | 2020-08-21 | 2020-12-01 | 华南农业大学 | Tung oil-based positive electrode binder for lithium-sulfur battery, positive electrode for lithium-sulfur battery and preparation method of positive electrode |
| CN113130897A (en) * | 2020-01-14 | 2021-07-16 | 深圳市优宝新材料科技有限公司 | Water-based binder and preparation method and application thereof |
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| CN107863534A (en) * | 2017-10-20 | 2018-03-30 | 电子科技大学 | A kind of polarity bonding agent applied to lithium-sulfur cell and preparation method thereof |
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| CN113889622B (en) * | 2020-07-01 | 2023-07-11 | 比亚迪股份有限公司 | Binder, negative electrode and lithium ion battery |
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| WO2018082181A1 (en) | 2018-05-11 |
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