CN103173161A - Preparation method of lithium ion battery cathode sheet adhesive emulsion - Google Patents
Preparation method of lithium ion battery cathode sheet adhesive emulsion Download PDFInfo
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- CN103173161A CN103173161A CN2013100749932A CN201310074993A CN103173161A CN 103173161 A CN103173161 A CN 103173161A CN 2013100749932 A CN2013100749932 A CN 2013100749932A CN 201310074993 A CN201310074993 A CN 201310074993A CN 103173161 A CN103173161 A CN 103173161A
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Abstract
The invention belongs to the technical field of lithium ion batteries, and especially relates to a preparation method of a lithium ion battery cathode sheet adhesive emulsion. The method comprises the following steps: adding distilled water, an emulsifier and a buffering agent into a polymerization kettle, heating to 70-80DEG C, fully stirring, and adding a first initiator and core monomers to prepare a core emulsion, wherein the mass proportion of monomers having a glass transition temperature higher than 20DEG C in all the core monomers is not lower than 25%; and adding shell monomers and a second initiator to the core emulsion to prepare the lithium ion battery cathode sheet adhesive emulsion having a core-shell structure, wherein the mass proportion of monomers having a glass transition temperature higher than 20DEG C in all the shell monomers is not higher than 20%. Compared with adhesive emulsions prepared through the prior art, the adhesive emulsion prepared through adopting the method has the advantages of hard inside and soft outside structure, high elastic modulus, good adhesion, and effective inhibition of the cathode sheet expansion, and allows batteries made through adopting the adhesive emulsion to have good low temperature performances.
Description
Technical field
The invention belongs to technical field of lithium ion, relate in particular to the preparation method of a kind of anode plate for lithium ionic cell by the caking agent emulsion.
Background technology
Lithium ion battery is since commercialization, because its energy density is high, operating voltage is high, memory-less effect, have extended cycle life and the plurality of advantages such as environmentally safe is widely used as the power supply of various mobile equipments, this also makes it enter the large-scale practical stage.
The performance of lithium ion battery can improve by the parts that improve battery, the performance of battery mainly depends on electrode, electrolytic solution and is contained in battery material wherein, the characteristic of electrode depends on active substance, collector and the binding agent that electrode comprises, wherein, the effect of binding agent is to provide between active substance and the bounding force between active substance and collector, electronics and lithium ion is moved reposefully in electrode and reduce the electrode internal resistance.
Originally, the Fluorine containing olefine polymkeric substance that caking agent is mainly used, for example, the Japanese patent application that publication number is Unexamined Patent 7-78056 disclose a kind of take Fluorine containing olefine polymkeric substance (as polyvinylidene difluoride (PVDF)) as binding agent, KETJEN carbon element be the technical scheme that active material is manufactured the negative electrode for lithium ion battery sheet.But the binding agent that the Fluorine containing olefine polymkeric substance of take is lithium ion battery material, in pole piece making processes, the volatilization of binder solution is contaminate environment but also endanger the personnel health not only, and also must collect also in addition suitable processing of solvent with special refrigerating apparatus after dry evaporating solvent, the Fluorine containing olefine polymkeric substance is expensive in addition, and this has increased production cost undoubtedly.In order to address these problems, people begin one's study and have developed lithium ion battery use caking agent as styrene butadiene polymkeric substance (SBR), the Japanese patent application that is JP2000106198 as application number discloses this aqueous adhesive of SBR, while using SBR as caking agent, generally also to add Xylo-Mucine (CMC) to be used in conjunction with.Through application verification for many years, the SBR/CMC aqueous binders obtains the market approval substantially.
But in recent years, along with the further raising of people to the requirement of the energy density of lithium ion battery, a large amount of alloy materials are used as negative material, now, the defect of SBR/CMC caking agent series just day by day exposes, and main manifestations is: cohesive force is too poor, for example, while when the negative pole system that this caking agent series is applied to mix 5% alloy (5% alloy material+95% graphite), being prepared into negative plate, the very easily demoulding of this negative plate, and then have influence on the cycle performance of battery.In addition, difference due to the affinity between Xylo-Mucine and each composition of electrolytic solution, cause the bath composition of polarity can't infiltrate in the active material particle of electrode, make the interface resistance of anode strip and the internal resistance of battery increase, this phenomenon shows more obviously when low temperature, and be embodied in battery and easily analyse lithium, and along with the increase of coating weight, the phenomenon that battery is analysed lithium is also more serious, has a strong impact on the safety performance of battery.
In view of this, the necessary preparation method of a kind of anode plate for lithium ionic cell by the caking agent emulsion that provide, the polymkeric substance that adopts caking agent prepared by the method to using to hang down polarity is as shell, the polymkeric substance of high polarity is as stratum nucleare, the shell of low polarity can significantly improve the flexibility of adhensive membrane and improve collector and active substance between and the adhesiving effect between active substance, the stratum nucleare of high polarity can significantly improve the force of cohesion of binding agent, thereby has effectively reduced the failure risk caused to binding agent because of the active substance overplumping in process of charging.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and a kind of anode plate for lithium ionic cell preparation method by the caking agent emulsion is provided, the polymkeric substance that adopts caking agent prepared by the method to using to hang down polarity is as shell, the polymkeric substance of high polarity is as stratum nucleare, the shell of low polarity can significantly improve the flexibility of adhensive membrane and improve collector and active substance between, and the adhesiving effect between active substance, the stratum nucleare of high polarity can significantly improve the force of cohesion of binding agent, thereby effectively reduced the failure risk caused to binding agent because of the active substance overplumping in process of charging.
In order to achieve the above object, the present invention adopts following technical scheme: the preparation method of caking agent emulsion for a kind of anode plate for lithium ionic cell, the solubility parameters of the dry glue that described caking agent emulsion drying forms afterwards is between 16-24(J/cm
3)
1/2between, the solubility parameters of some glue is higher than 24(J/cm
3)
1/2, due to solubility parameters and (the δ ≈ 29 (J/cm of the carbonic ether in electrolytic solution of caking agent emulsion
3)
1/2) solubility parameters approach, easily cause binder swells excessive, make adhesive failure, and the solubility parameters of some glue is lower than 16(J/cm
3)
1/2, can cause binding agent and electrolytic solution compatibility too poor, make the battery poor performance at low temperatures.Its preparation method comprises the following steps: the first step, by distilled water, emulsifying agent and buffer reagent sodium bicarbonate add in the polymeric kettle of crossing through nitrogen replacement, then be warming up to 50-90 ℃, after fully stirring, add the first initiator and nuclear monomer, stir 10min-16h under 50-90 ℃ after, insulation 10min-2h, make the core emulsion, the mass ratio that second-order transition temperature in described nuclear monomer (Tg) accounts for the nuclear monomer total amount higher than the monomer of 20 ℃ is not less than 25%, described distilled water, described emulsifying agent, described buffer reagent sodium bicarbonate, the mass ratio of described the first initiator and described nuclear monomer is (100-2000): (0.1-5): (0.1-1): (0.05-2): 100.
Second step, in 1-5h, drip shell monomers and the second initiator in the core emulsion made to the first step, at 50-90 ℃ of lower insulated and stirred 1-8h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, the mass ratio that in described shell monomers, second-order transition temperature accounts for the shell monomers total amount higher than the monomer of 20 ℃ is not higher than 20%, and the mass ratio of described the second initiator and described shell monomers is (0.01-1.5): 100.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, the general structure of described nuclear monomer and shell monomers is CH
2=CR
1r
2, R wherein
1for H or CH
3, R
2for H, CH
3, CONH
2, COOCH
3, COOCH
2cH
3, O-CH
2cH
2-OH, C
6h
5, CN, COOCH
3, COOCH
2cH
3, COOC
4h
9or COOC
8h
17.
Experience shows, all Tg, approaching room temperature or the polymkeric substance more than room temperature, will show higher hardness under normal temperature.Otherwise Tg is lower than 20 ℃, normal temperature is next shows as soft outward appearance.On this basis, monomer can be divided into to hard monomer and the large class of soft monomer two.Wherein, soft monomer commonly used and second-order transition temperature thereof (being shown in bracket) are: β-dimethyl-aminoethylmethacrylate (5 ℃), methyl acrylate (8 ℃), ethyl propenoate (22 ℃), butyl acrylate (54 ℃), Isooctyl acrylate monomer (88 ℃), Hydroxyethyl acrylate (15 ℃), 2-hydroxypropyl acrylate (7 ℃) and ethyl acrylate (70 ℃).Common hard monomer and second-order transition temperature thereof (being shown in bracket) are: methacrylic acid (130 ℃), methyl methacrylate (105 ℃), butyl methacrylate (20 ℃), Isooctyl methacrylate (55 ℃), hydroxyethyl methylacrylate (55 ℃), methacrylic acid-2-hydroxypropyl acrylate (26 ℃), vinylformic acid (106 ℃), acrylamide (153 ℃) and vinyl cyanide (96 ℃).
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, described emulsifying agent is sodium lauryl sulphate and/or polyoxyethylene octylphenol ether.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, described initiator is at least one in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate and dibenzoyl peroxide.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, the second-order transition temperature of the core emulsion that the first step makes is 20 ℃-60 ℃; The anode plate for lithium ionic cell with nucleocapsid structure that second step makes is with in the caking agent emulsion, and the second-order transition temperature of shell structure is-30 ℃-25 ℃.The second-order transition temperature of core emulsion is too high, easily causes the negative plate embrittlement; And the second-order transition temperature of shell structure is too low, easily stick again cold pressing roller while colding pressing negative plate, cause the excellent rate of production of negative plate to reduce.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, after the caking agent emulsion that second step is made is prepared into dry film, the ionic conductivity of described dry film is not less than 10
-6s/cm, the too low meeting of ionic conductivity causes the internal resistance of cell to become large, and then causes the battery deteriorated low temperature performance.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, the solid content of the caking agent emulsion that second step makes is 5%-50%, viscosity at normal temperatures is 10 mPas-10000 mPas.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, the Young's modulus of the dry glue that the 100um that the caking agent emulsion drying that second step makes forms afterwards is thick is not less than 300MPa, Young's modulus is too low, the cohesive force that means caking agent is too poor, easily causes the generation of the problems such as the pole piece demoulding.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, also added cross-linking monomer in the first step, the mass percent that described cross-linking monomer accounts for described core emulsion is less than or equal to 10%, the mass percent of cross-linking monomer is too high, easily cause negative plate fragility excessive, be unfavorable for the processing of negative plate.The interpolation of cross-linking monomer has improved the cross-linking density of polymkeric substance itself, and then has improved the force of cohesion of binding agent.
A kind of improvement as anode plate for lithium ionic cell of the present invention by the preparation method of caking agent emulsion, described cross-linking monomer is at least one in Vinylstyrene, N hydroxymethyl acrylamide and Hydroxyethyl acrylate.
With respect to prior art, the polymkeric substance that the core core of the caking agent emulsion that adopts method of the present invention to prepare is high polarity, the polymkeric substance that shell is low polarity (this caking agent emulsion has interior hard outer soft constructional feature).Wherein, thereby the shell of low polarity can significantly improve the flexibility of adhensive membrane on the one hand to be improved between collector and active substance and the adhesiving effect between active substance, on the other hand, the shell of low polarity is conducive to reduce the surface tension of cathode size, improve the wettability of cathode size anticathode collector, improve coating quality.In addition, polymkeric substance swelling in electrolytic solution of low polarity is little, thereby has improved the stability of binding agent in electrolyte system, improves the cohesive force of caking agent, has effectively prevented the generation of the problems such as adhesive failure.
And the polymkeric substance of high polarity can significantly improve the force of cohesion of binding agent self as the core core, increase Young's modulus, thereby effectively reduced the failure risk caused to binding agent because of the active substance overplumping in process of charging.High polar polymer swelling in electrolytic solution is relatively large on the other hand, is conducive to improve the ionic conductivity of binding agent, thereby promotes the cryogenic discharging characteristic of lithium ion battery.
And the solubility parameters δ of the dry glue that forms afterwards of caking agent emulsion drying is between 16-24(J/cm
3)
1/2between, (the δ ≈ 29 (J/cm of the carbonic ether in this caking agent and electrolytic solution
3)
1/2) solubility parameters of equal solvent differs larger, so it can not be dissolved in the carbonic ether isopolarity solvent in electrolytic solution, thereby guaranteed the pole piece performance.
The accompanying drawing explanation
Fig. 1 is that in the present invention, numbering is respectively the pole piece bounce-back rate in each operation process prepared at battery by the negative plate of N1-N5 and ND1 and ND2.
In Fig. 2 the present invention, numbering is respectively C1, C2, CD1, and the cycle diagram of the lithium ion battery of CD2 under 45 ℃.
Embodiment
Below in conjunction with specific embodiment and accompanying drawing, content of the present invention is further detailed, but protection scope of the present invention is not limited only to the described content of embodiment.
Embodiment 1, the preparation method of caking agent emulsion for a kind of anode plate for lithium ionic cell that the present embodiment provides, and the solubility parameters of the dry glue that this caking agent emulsion drying forms afterwards is 20(J/cm
3)
1/2between, its preparation method comprises the following steps: the first step, by 241.5 parts of distilled water, 1.8 part emulsifier sodium lauryl sulfate and 0.6 part of polyoxyethylene octylphenol ether and 0.5 part of buffer reagent sodium bicarbonate add in the polymeric kettle of crossing through nitrogen replacement, then be warming up to 80 ℃, after fully stirring, add 0.3 part of first initiator potassium persulfate and nuclear monomer, the vinylbenzene that nuclear monomer is 35 parts (second-order transition temperature of polystyrene is about 100 ℃), the vinyl cyanide of 10 parts (second-order transition temperature of polyacrylonitrile is about 96 ℃), the mixture of the vinylformic acid (polyacrylic second-order transition temperature is 106 ℃) of the butyl acrylate of 13 parts (second-order transition temperature of butyl polyacrylate for-55 ℃) and 1 part, stir 10min under 90 ℃ after, insulation 1h, make the core emulsion of second-order transition temperature between 20 ℃～60 ℃.
Second step, in 3h, drip the second initiator potassium persulfate of shell monomers and 0.3 part in the core emulsion made to the first step, at 70 ℃ of lower insulated and stirred 3h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, wherein, the second-order transition temperature of shell structure is between-30 ℃-25 ℃, the ethyl propenoate that shell monomers is 28 parts (second-order transition temperature of polyethyl acrylate is-22 ℃), the mixture of the butyl acrylate of the Hydroxyethyl acrylate of 3 parts (second-order transition temperature of Poly(Hydroxyethyl Methacrylate) is-15 ℃) and 10 parts (second-order transition temperature of butyl polyacrylate is-54 ℃).
Experiment shows, the solid content of the caking agent emulsion that second step makes is 30%.
Embodiment 2, the preparation method of caking agent emulsion for a kind of anode plate for lithium ionic cell that the present embodiment provides, and the solubility parameters of the dry glue that this caking agent emulsion drying forms afterwards is 22(J/cm
3)
1/2between, its preparation method comprises the following steps: the first step, by 102.1 parts of distilled water, 1.5 part emulsifier sodium lauryl sulfate and 0.3 part of buffer reagent sodium bicarbonate add in the polymeric kettle of crossing through nitrogen replacement, then be warming up to 85 ℃, after fully stirring, add 0.5 part of first initiator ammonium persulfate and nuclear monomer, the acrylamide that nuclear monomer is 12 parts (second-order transition temperature of polyacrylamide is about 153 ℃), the vinylbenzene of 5 parts (second-order transition temperature of polystyrene is about 100 ℃), the mixture of the Isooctyl acrylate monomer of the butyl acrylate of 23 parts (second-order transition temperature of butyl polyacrylate is-55 ℃) and 36 parts (second-order transition temperature of the different monooctyl ester of polyacrylic acid is-88 ℃), stir 12h under 70 ℃ after, insulation 30min, make the core emulsion of second-order transition temperature between 20 ℃-60 ℃.
Second step, in 4h, drip the second initiator ammonium persulfate of shell monomers and 0.8 part in the core emulsion made to the first step, at 60 ℃ of lower insulated and stirred 7h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, wherein, the second-order transition temperature of shell structure is between-30 ℃-25 ℃, the Hydroxyethyl acrylate that shell monomers is 6 parts (second-order transition temperature of Poly(Hydroxyethyl Methacrylate) is-15 ℃), the mixture of the vinylformic acid (polyacrylic second-order transition temperature is 106 ℃) of the ethyl propenoate of 12 parts (second-order transition temperature of polyethyl acrylate for-22 ℃) and 5 parts.
Experiment shows, the solid content of the caking agent emulsion that second step makes is 50%.
Embodiment 3, the preparation method of caking agent emulsion for a kind of anode plate for lithium ionic cell that the present embodiment provides, and the solubility parameters of the dry glue that this caking agent emulsion drying forms afterwards is 18(J/cm
3)
1/2between, its preparation method comprises the following steps: the first step, by 918.9 parts of distilled water, 1 part of emulsifying agent polyoxyethylene octylphenol ether and 0.1 part of buffer reagent sodium bicarbonate add in the polymeric kettle of crossing through nitrogen replacement, then be warming up to 75 ℃, after fully stirring, add 0.8 part of first initiator Diisopropyl azodicarboxylate and nuclear monomer, the acrylamide that nuclear monomer is 9 parts (second-order transition temperature of polyacrylamide is about 153 ℃), the mixture of the methyl acrylate (second-order transition temperature of polymethyl acrylate is 8 ℃) of the Isooctyl acrylate monomer of 26 parts (second-order transition temperature of the different monooctyl ester of polyacrylic acid is about-88 ℃) and 15 parts, stir 12h under 70 ℃ after, insulation 2h, make the core emulsion of second-order transition temperature between 20 ℃-60 ℃.
Second step, in 2h, drip the second initiator Diisopropyl azodicarboxylate of shell monomers and 0.2 part in the core emulsion made to the first step, at 50 ℃ of lower insulated and stirred 8h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, wherein, the second-order transition temperature of shell structure is between-30 ℃-25 ℃, the vinyl cyanide that shell monomers is 10 parts (second-order transition temperature of polyacrylonitrile is 96 ℃), the Isooctyl acrylate monomer of 22 parts (second-order transition temperature of the different monooctyl ester of polyacrylic acid is-88 ℃), the mixture of the vinylformic acid (polyacrylic second-order transition temperature is 106 ℃) of the butyl acrylate of 10 parts (second-order transition temperature of butyl polyacrylate for-22 ℃) and 8 parts.
Experiment shows, the solid content of the caking agent emulsion that second step makes is 10%.
Embodiment 4, the preparation method of caking agent emulsion for a kind of anode plate for lithium ionic cell that the present embodiment provides, and the solubility parameters of the dry glue that this caking agent emulsion drying forms afterwards is 16(J/cm
3)
1/2between, its preparation method comprises the following steps: the first step, by 332.1 parts of distilled water, 2 parts of emulsifying agent polyoxyethylene octylphenol ethers and 0.7 part of buffer reagent sodium bicarbonate add in the polymeric kettle of crossing through nitrogen replacement, then be warming up to 82 ℃, after fully stirring, the cross-linking monomer Vinylstyrene that adds 1 part of first initiator dibenzoyl peroxide and nuclear monomer and 6 parts, the acrylamide that nuclear monomer is 3 parts (second-order transition temperature of polyacrylamide is about 153 ℃), the Isooctyl acrylate monomer of 10 parts (second-order transition temperature of the different monooctyl ester of polyacrylic acid is about-88 ℃), the vinyl cyanide of 13 parts (second-order transition temperature of polyacrylonitrile is 96 ℃), the mixture of the Hydroxyethyl acrylate of the methyl methacrylate of 5 parts (second-order transition temperature of polymethylmethacrylate is 105 ℃) and 42 parts (second-order transition temperature of Poly(Hydroxyethyl Methacrylate) is-15 ℃), stir 16h under 50 ℃ after, insulation 10min, make the core emulsion of second-order transition temperature between 20 ℃-60 ℃.
Second step, in 1h, drip the second initiator dibenzoyl peroxide of shell monomers and 1 part in the core emulsion made to the first step, at 90 ℃ of lower insulated and stirred 1h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, wherein, the second-order transition temperature of shell structure is between-30 ℃-25 ℃, the Isooctyl acrylate monomer that shell monomers is 15 parts (second-order transition temperature of the different monooctyl ester of polyacrylic acid is-88 ℃), the mixture of the vinylformic acid (polyacrylic second-order transition temperature is 106 ℃) of the butyl acrylate of 10 parts (second-order transition temperature of butyl polyacrylate for-22 ℃) and 2 parts.
Experiment shows, the solid content of the caking agent emulsion that second step makes is 25%.
Second step, in 5h, drip shell monomers and 1 part of Potassium Persulphate and 1 part of ammonium persulphate in the core emulsion made to the first step, at 70 ℃ of lower insulated and stirred 2h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, wherein, the second-order transition temperature of shell structure is between-30 ℃-25 ℃, the Isooctyl acrylate monomer that shell monomers is 20 parts (second-order transition temperature of the different monooctyl ester of polyacrylic acid is-88 ℃), the mixture of the acrylamide (second-order transition temperature of polyacrylamide is 153 ℃) of the butyl methacrylate of 5 parts (second-order transition temperature of poly-n-butyl methacrylate is 105 ℃) and 5 parts.
Experiment shows, the solid content of the caking agent emulsion that second step makes is 15%.
In order to detect the performance of the caking agent emulsion that adopts method of the present invention to prepare, binding agent emulsion prepared by the method that adopts embodiment 1-5 and commercially available SBR emulsion have carried out viscosity test, the second-order transition temperature test, ionic conductivity test and modulus test, wherein the method for modulus test is as follows: the binding agent emulsion is coated on polyfluortetraethylene plate, oven dry obtains the diaphragm of the about 100um of thickness, be trimmed to the rectangle small pieces of 6cm * 1cm, be loaded on omnipotent puller system, with the test in 50mm/min, record value of thrust and strain value, obtain the stress-strain(ed) curve of binding agent, modulus=stress/strain wherein, acquired results is in Table 1.
Table 1: the performance of the binding agent of different embodiment/Comparative Examples.
As can be seen from Table 1: the viscosity of the caking agent emulsion that adopts method of the present invention to prepare is large, ionic conductivity is higher and Young's modulus is high, thereby improve between collector and active substance and the adhesiving effect between active substance, effectively suppress the expansion of negative plate, promote the cryogenic discharging characteristic of lithium ion battery.
Caking agent emulsion prepared by the method that adopts embodiment 1 and 3 to 5 respectively with natural graphite, Xylo-Mucine and conductive carbon (wherein, the mass ratio of caking agent emulsion, natural graphite, Xylo-Mucine and conductive carbon is 4:93:1.5:1.5) add in distilled water, make cathode size after stirring, then by each slurry, be coated on respectively on Copper Foil, drying and cold pressing after make negative plate, the gained negative plate is numbered respectively N1 and N3-N5.
The caking agent emulsion that will prepare by the method for embodiment 2 and natural graphite, silicon-carbon alloy, Xylo-Mucine and conductive carbon (wherein; the mass ratio of SBR emulsion, natural graphite, silicon-carbon alloy and conductive carbon is 4:82:11:1.5:1.5) add in distilled water; make cathode size after stirring; then slurry is coated on Copper Foil; drying and cold pressing after make negative plate, be numbered N2.
As a comparison, commercially available SBR emulsion and natural graphite, Xylo-Mucine and conductive carbon (wherein; the mass ratio of SBR emulsion, natural graphite, Xylo-Mucine and conductive carbon is 4:93:1.5:1.5) are added in distilled water; make cathode size after stirring; then slurry is coated on Copper Foil; drying and cold pressing after make negative plate, the gained negative plate is numbered ND1.
As a comparison, commercially available SBR emulsion, natural graphite, silicon-carbon alloy, Xylo-Mucine and conductive carbon (wherein; the mass ratio of SBR emulsion, natural graphite, silicon-carbon alloy and conductive carbon is 4:82:11:1.5:1.5) are added in distilled water; make cathode size after stirring; then slurry is coated on Copper Foil; drying and cold pressing after make negative plate, be numbered ND2.
The negative plate that numbering is respectively to N1-N5 and ND1 and ND2 is tested as follows: (1) pole piece cohesive force test: get the negative plate that numbering is respectively N1-N5 and ND1 and ND2, be cut into the rectangle small pieces of 20mm * 10cm size, the two-sided gluing wide with 20mm is on clean stainless steel plate, adopt the peeling force of 180 ° of puller system test pole pieces, the puller system draw speed is 50mm/min, the results are shown in table 2.
(2) pole piece electrolyte resistance improving soaking test: get the negative plate that numbering is respectively N1-N5 and ND1 and ND2, be cut into the rectangle small pieces of 20mm * 10cm size, be placed in electrolytic solution, airtight being placed in 60 ℃ of baking ovens, take out each negative plate after 96 hours, adopt the method test pole piece cohesive force of above-mentioned pole piece cohesive force test, the results are shown in table 2.
In addition, the resistance that also numbering is respectively to the negative plate of N1-N5 and ND1 and ND2 is tested, and acquired results is in Table 2.
Table 2: numbering is respectively cohesive force and the resistance of the negative plate of N1-N5 and ND1 and ND2.
As can be seen from Table 2: adopt binding agent emulsion prepared by method of the present invention to can be used for preparing negative plate, and the negative plate obtained compares with adopting commercially available SBR emulsion as the negative plate of caking agent, there are the characteristics such as the strong and membrane resistance of bonding force is little.And, under the same terms, the negative plate that adopts binding agent emulsion prepared by method of the present invention to prepare is after electrolytic solution soaks, cohesive force is apparently higher than the negative plate that adopts commercially available SBR emulsion as caking agent.
(3) pole piece bounce-back test: get the negative plate that numbering is respectively N1-N5 and ND1 and ND2, with milscale test pole piece thickness, as the pole piece initial thickness.Then individual negative plate is made to battery core with positive plate and barrier film through the coiling operation respectively, then battery core is placed in to packaging foil, after injecting electrolytic solution, changed into, capacity, make lithium ion battery, and number consecutively is C1-C5 and CD1 and CD2.In the battery preparation process, before toasting afterwards, reel at negative plate successively, the shaping of battery core fixture, battery completely is charged to 4.35V (100%SOC) for the first time, battery is discharged to 3.0V (0%SOC) for the first time, and voltage is several stages test such as 3.85V (50%SOC) negative plate thickness, calculate the bounce-back rate of each pole piece under different states, acquired results is shown in Fig. 1.
As shown in Figure 1, the caking agent emulsion that adopts method of the present invention to prepare is compared as the negative plate of caking agent with traditional employing SBR emulsion as the negative plate of caking agent, and the bounce-back rate of same phase is obviously low.This shows that the caking agent emulsion that adopts method of the present invention to prepare can suppress the expansion of negative plate effectively.
Getting respectively the lithium ion battery that is numbered C1 and CD1 is that sample carries out the low-temperature performance test: under 10 ℃, with 0.7C multiplying power charging, 0.5C multiplying power discharging, circulate after 10 times, disassemble battery, observe negative terminal surface and analyse the lithium situation.Result shows: the negative plate surface be numbered in the battery of C1 not have to find to analyse the phenomenon of lithium, and the surface that is numbered the negative plate in the battery of CD1 has very significantly analyses the appearance of lithium phenomenon.This caking agent emulsion that shows to adopt method of the present invention to prepare has low-temperature performance preferably as the lithium ion battery of caking agent.
To the battery that is numbered C1, C2, CD1 and CD2 at 45 ℃ with 0.7 multiplying power charging, the 0.5C multiplying power discharging, circulate after 400 times, the results are shown in Figure 2.As seen from Figure 2, in the graphite system, the caking agent emulsion that adopts method of the present invention to prepare is little as the cycle performance difference of the lithium ion battery of caking agent with the commercially available SBR emulsion of employing as the lithium ion battery of caking agent, but in the system that has added alloy, adopt commercially available SBR emulsion the phenomenon of circulation diving to occur as the lithium ion battery of caking agent, and the caking agent emulsion that adopts method of the present invention to prepare still remains on 87% as the capability retention of the lithium ion battery of caking agent, this caking agent emulsion that shows to adopt method of the present invention to prepare has safe and reliable and characteristics that have extended cycle life as the lithium ion battery of caking agent.
It should be noted that, the announcement of book and elaboration according to the above description, those skilled in the art in the invention can also be changed and be revised above-mentioned embodiment.Therefore, the present invention is not limited to embodiment disclosed and described above, also should be in the protection domain of claim of the present invention to equivalent modifications more of the present invention and change.In addition, although used some specific terms in this specification sheets, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (10)
1. the preparation method of an anode plate for lithium ionic cell use caking agent emulsion, is characterized in that, the solubility parameters of the dry glue that described caking agent emulsion drying forms afterwards is between 16-24(J/cm
3)
1/2between, its preparation method comprises the following steps:
The first step, by distilled water, emulsifying agent and buffer reagent sodium bicarbonate add in the polymeric kettle of crossing through nitrogen replacement, then be warming up to 70-80 ℃, after fully stirring, add the first initiator and nuclear monomer, stir 10min-16h under 70-80 ℃ after, insulation 10min-2h, make the core emulsion, the mass ratio that in described nuclear monomer, second-order transition temperature accounts for the nuclear monomer total amount higher than the monomer of 20 ℃ is not less than 25%, described distilled water, described emulsifying agent, described buffer reagent sodium bicarbonate, the mass ratio of described the first initiator and described nuclear monomer is (100-2000): (0.1-5): (0.1-1): (0.05-2): 100,
Second step, in 1-5h, drip shell monomers and the second initiator in the core emulsion made to the first step, at 50-90 ℃ of lower insulated and stirred 1-8h, discharging after cooling, make the caking agent emulsion of the anode plate for lithium ionic cell with nucleocapsid structure, the mass ratio that in described shell monomers, second-order transition temperature accounts for the shell monomers total amount higher than the monomer of 20 ℃ is not higher than 20%, and the mass ratio of described the second initiator and described shell monomers is (0.01-1.5): 100.
2. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: the general structure of described nuclear monomer and shell monomers is CH
2=CR
1r
2, R wherein
1for H or CH
3, R
2for H, CH
3, CONH
2, COOCH
3, COOCH
2cH
3, O-CH
2cH
2-OH, C
6h
5, CN, COOCH
3, COOCH
2cH
3, COOC
4h
9or COOC
8h
17.
3. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: described emulsifying agent is sodium lauryl sulphate and/or polyoxyethylene octylphenol ether.
4. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: described the first initiator and described the second initiator are at least one in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate and dibenzoyl peroxide.
5. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: the second-order transition temperature of the core emulsion that the first step makes is 20 ℃-60 ℃; The anode plate for lithium ionic cell with nucleocapsid structure that second step makes is with in the caking agent emulsion, and the second-order transition temperature of shell structure is-30 ℃-25 ℃.
6. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: after the caking agent emulsion that second step is made is prepared into dry film, the ionic conductivity of described dry film is not less than 10
-6s/cm.
7. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: the solid content of the caking agent emulsion that second step makes is 5%-50%, viscosity at normal temperatures is 10 mPas-10000 mPas.
8. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: the Young's modulus of the dry glue that the 100um that the caking agent emulsion drying that second step makes forms afterwards is thick is not less than 300MPa.
9. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 1, it is characterized in that: also added cross-linking monomer in the first step, the mass percent that described cross-linking monomer accounts for described core emulsion is less than or equal to 10%.
10. the preparation method of caking agent emulsion for anode plate for lithium ionic cell according to claim 9, it is characterized in that: described cross-linking monomer is at least one in Vinylstyrene, N hydroxymethyl acrylamide and Hydroxyethyl acrylate.
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