CN109755582A - Lithium ion cell positive polyimide binder and the preparation method and application thereof - Google Patents
Lithium ion cell positive polyimide binder and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses lithium ion cell positive polyimide binders and the preparation method and application thereof；The polyimide binder contains-SO simultaneously2‑、‑CF3, four kinds of groups of-CO- and-O-；When preparation, diamine monomer is dissolved in solvent, stirring to addition catalyst and dianhydride monomer after completely dissolution, moisture is taken out of by stream of nitrogen gas, stirs 4~10h, heating dehydration imidizate at room temperature, reactant is poured into methanol or ethyl alcohol after cooling, obtains polyimide polymer；Polyimides of the invention is good to electrolyte wetability, with more stable conjugated system, it is used as lithium ion cell positive binder, prepared lithium ion battery impedance is low, stable electrochemical property, it is not easy to degrade as battery charging and discharging recycles, high rate performance and cycle performance are enhanced, overcharge safety is improved, effectively extends the service life of battery.
Description
Technical field
The invention belongs to technical field of lithium ion, specifically design a kind of lithium ion cell positive binder, use
Lithium ion cell positive of the binder and preparation method thereof.
Background technique
Lithium ion battery has that energy density is high, have extended cycle life, self-discharge rate is low and the excellent spy such as memory-less effect
Property, traditional lead acid batteries and ickel-cadmium cell are gradually substituted, is widely used in portable electronic device.In order to further expand
The business application of big lithium ion battery proposes significant challenge to high-power output performance and security performance aspect.Wherein, lithium from
Many chemical properties of sub- battery, such as the performance of stability, irreversible capacity loss performance and binder are closely related.
Binder is the important component of lithium ion battery plus-negative plate, is a kind of electrode active material layer to be adhered to collection
High molecular polymer on fluid, main function is that each component in electrode is made to bond closely and stablize pole piece structure, to alleviate
The expansion and contraction of pole piece in battery charge and discharge process, and reduce the resistance of electrode.
Currently, most popular binder is PVDF in lithium ion cell positive, but expensive, flexibility is poor,
It is swollen cannot to alleviate volume contraction of battery during embedding and removing mainly from interface interaction power well for its cementation
It is swollen, so that the long-term cycle performance and security performance to battery have some impact on.Polyimide material have structure diversity,
The characteristics such as steady chemical structure, good mechanical performance, as the binder in lithium ion cell positive, high to development capacity,
Stable cycle performance and the polyimides having a safety feature are of great significance.
Currently, application study of the polyimide binder in silicium cathode is relatively broad, but its research is mostly from polyamides Asia
The good mechanicalness of amine, thermal stability and caking property are that starting point makes to design the polyimide binder of corresponding construction
Prepared polyimides adapts to volume change of the silicium cathode in charge and discharge process, such as Kim J S, Choi W, Cho K
Y,et al.Effect of polyimide binder on electrochemical characteristics of
surface-modified silicon anode for lithium ion batteries[J].Journal of Power
Sources,2013,244:521-526、Choi J,Kim K,Jeong J,et al.Highly Adhesive and
Soluble Copolyimide Binder:Improving the Long-Term Cycle Life of Silicon
Anodes in Lithium-Ion Batteries[J].ACS Appl Mater Interfaces,2015,7(27):
The research about polyimides in terms of silicium cathode such as 14851-14858.
But it is less about research of the polyimides in terms of lithium ion cell positive, and most of research is set out
Point is also similar to silicium cathode, only considers excellent mechanicalness, thermal stability and the caking property of polyimides, such as Choi J,
Ryou M-H,Son B,et al.Improved high-temperature performance of lithium-ion
batteries through use of a thermally stable co-polyimide-based cathode binder
[J] .Journal of Power Sources, 2014,252:138-143 etc., and about different functional groups to electrode lithium ion
It is mobility, less with the research of compatibility of electrolyte etc., and the performances such as mobility and the electrochemistry of electrode are closely bound up.It is existing
Have and contains-SO in technology simultaneously2-、-CF3,-CO- and-O- this 4 kinds of groups lithium ion cell positive binder there has been no public affairs
It opens, in electrode and lithium ion binding ability, ion transferring capability, electrochemical stability, thermal stability, in organic solvent molten
Xie Li, electrode to the absorbability of electrolyte, electrode impedance and flexibility etc. there are the deficiency of some aspects, it is comprehensive
It can be to be improved.
Summary of the invention
Technology of the invention provides one kind mainly for the deficiency in terms of the binder for being applied to lithium ion battery at present
Positive binder, the binder cohesive force is strong, enhances electrode and lithium ion binding ability, ion transferring capability, electrochemistry are steady
Qualitative, thermal stability and dissolving power in organic solvent, and absorption of the electrode to electrolyte is improved, electrode impedance is reduced,
The flexibility for increasing pole piece ensure that the cyclical stability and overcharge safety of lithium ion battery.
Another object of the present invention is to provide described lithium ion cell positive polyimide binder and preparation method thereof.
Further object of the present invention is to provide the lithium ion cell positive using polyimide binder preparation.
The sulfuryl (- SO contained in binder polymer unit of the present invention2) there is strong electron attraction and hygroscopicity, increase
Forceful electric power pole and lithium ion binding ability, and absorption of the electrode to electrolyte is improved, reduce electrode impedance.Meanwhile-SO2Presence
The stability of polymer conjugate system is increased, to keep electrode structure more stable in charge and discharge process.Contain in binder
Some trifluoromethyl (- CF3) enhance ion transferring capability, electrochemical stability, thermal stability and in organic solvent
Solvability.The caking property and flexibility of ketone group (- CO-) and ehter bond (- O-) the enhancing polyimides contained in structure, ensure that
The cyclical stability and overcharge safety of lithium ion battery.
The polyimides that the present invention designs is guaranteeing its dissolubility, caking property, mechanical performance and while thermal stability,
Introduce-the SO with stronger electron attraction2, with stronger hygroscopicity, the compatible of electrode and electrolyte can be increased
Property, electrode is easier to penetrate into electrode interior in charge and discharge process, improves ability of the electrode in conjunction with lithium ion, reduces electrode
Impedance, improve the high rate performance of battery, and-SO2Make designed polyimides that there is more stable conjugated body
System, to increase, battery is more stable in charge and discharge process, effectively extends the service life of battery.The present invention by with quotient
The PVDF binder of industry compares, consider caking property, mechanical performance, it is heat-staple simultaneously, inquired into through introducing-SO2-
To improve the new way of lithium iron phosphate positive material chemical property.
The present invention realizes technical solution used by above-mentioned purpose are as follows:
A kind of lithium ion cell positive binder contains-SO2-、-CF3,-CO- and-O- polyimide polymer,
Its structural formula such as following formula (1):
Wherein, m:n=5:1~1:5 in the polyimides；Degree of polymerization m+n is the integer of 100-5000；
The R1、R2And R3Structural formula be as follows:
Wherein, R1、R2、R3Structure by selection, so that the positive electrode binder is contained-SO simultaneously2-、-CF3-、-CO-
With four kinds of groups of-O-.
The preparation method of lithium ion cell positive binder: diamine monomer is dissolved in solvent, and stirring is to filling
Catalyst and dianhydride monomer is added after dividing dissolution, moisture is taken out of by stream of nitrogen gas, stirs 4~10h at room temperature, heating is dehydrated acyl
Imidization pours into reactant in methanol or ethyl alcohol after cooling, and obtains fibrous white or the polymerization of light yellow polyimides
Object；
The diamine monomer is 4,4'- diaminobenzophenone, 4,4'- diaminodiphenyl ether, 4,4'- diamino hexichol
Bis- (2- trifluoromethyl -4- amino benzoyl) benzene of sulfone, 2,2'- bis trifluoromethyl -4,4'- diamino hexichol, 1,4-, 1,4- are bis-
One of (2- trifluoromethyl -4- aminobenzene sulfuryl) benzene and bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4- are a variety of；
The dianhydride monomer be 3,3',4,4' benzophenone tetracarboxylic dianhydride, 4,4'- biphenyl ether dianhydride, 3,3', 4,
4'- diphenyl sulfone tetracarboxylic dianhydride, 2,2'- bis trifluoromethyl -3,3', 4,4'- diphenyl ether tetraformic dianhydride, the bis- (2- tri- of 1,4-
Methyl fluoride -3,3',4,4' benzophenone tetracarboxylic dianhydride) benzene, bis- (2- trifluoromethyl -3,3', the 4,4'- diphenyl sulfones four of 1,4-
Carboxylic acid dianhydride) one of benzene and bis- (2- trifluoromethyl -4,4'- biphenyl ether dianhydride) benzene of 1,4- or a variety of；
The solvent is metacresol, m-Chlorophenol or parachlorphenol；
The catalyst is quinoline, isoquinolin or tertiary amine.
To further realize the object of the invention, it is preferable that the molar ratio of the diamine monomer and dianhydride monomer be 1:1~
1:1.02。
Preferably, the catalyst accounts for the 0.2~0.5% of solvent volume；It is molten after addition catalyst and dianhydride monomer
The solid content of diamines and dianhydride is 5%~20% in liquid.
Preferably, the temperature of the described heating dehydration imidizate is 170~210 DEG C, heating dehydration imidizate when
Between be 5~20h.
A kind of lithium ion cell positive prepared using the binder: the anode includes current collector aluminum foil and painting
The active material layer on the current collector aluminum foil surface is overlayed on, the active material layer includes positive active material, conductive agent and institute
The binder stated；The positive active material content is 2mg cm-2~4mg cm-2；Binder matter in the active material layer
Measuring content is 1%~15%；Conductive agent mass content is 3%~20%. in the active material layer
Preferably, the positive active material is LiFePO4 (LiFePO4), cobalt acid lithium (LiCoO2), LiMn2O4
(LiMn2O4), lithium nickelate (LiNiO2) and tertiary cathode material nickle cobalt lithium manganate (Li (NiCoMn) O2) one of or it is a variety of
Kind.
Preferably, the conductive agent be acetylene black, superconduction carbon black (super P), carbon nanotube, graphene with section's qin
It is one of black or a variety of.
The preparation method of the lithium ion cell positive, includes the following steps:
1) it takes binder heating stirring to be dissolved in solvent, obtains binder solution；It takes the powder of positive active material and leads
Electric agent ground and mixed uniformly afterwards be added binder solution in, by add solvent adjustment compounding substances viscosity be 2000~
10000mpa s, obtains active material slurry；The solvent is N,N-dimethylformamide (DMF), N, N- dimethyl second first
Amide (DMAC) or N-Methyl pyrrolidone (NMP)；
2) active material slurry is coated uniformly on aluminium foil, is compacted after dry, obtains lithium ion cell positive.
Preferably, the mass concentration that solution is bonded described in step 1) is 20%~40%；The drying be 60 DEG C~
120 DEG C of vacuum dryings.
Compared to existing technology, the present invention has the advantage that
1. maintaining polymer segment containing-CO- and-O- in the polyimide structures of synthesis with good flexibility, mentioning
The high caking property of polymer, makes in electrode that each component bonding is even closer, improves the cyclical stability of electrode and overcharges peace
Quan Xing.
2.-the SO contained in polyimide structural units2There is strong electron attraction and hygroscopicity, enhance electrode and lithium
Ion binding capacity improves absorption of the electrode to electrolyte, reduces electrode impedance, and-SO2Enhance polyimides
The stability of conjugated structure enables it to be promoted in the stability of electrode charge and discharge process electrode structure.
3.-the CF contained in polyimide structural units3Enhance ion transferring capability, electrochemical stability, thermostabilization
Property and solvability in organic solvent；
4. the polyimide binder synthesized using the present invention, prepared electrode has lesser impedance value, in 0.1C
Current density under recycle 3 activation after, impedance value is 30 Ω, and uses the impedance value of commercialized PVDF binder for 88
Ω。
5. electrode prepared by the polyimide binder that the present invention synthesizes has preferable overcharge safety energy, to mention
The high safety in utilization of lithium ion battery.The electrode of commercialized PVDF binder preparation is crossed used by being charged to 5V from 2.5V
Time 13.6h, and use synthesized polyimide binder it overcharges the time and will elongate to 29.3h.
6. electrode prepared by the polyimide binder that the present invention synthesizes has excellent high rate performance and cycle performance,
The case where making lithium ion battery be suitable for charge and discharge under high current density, and improve its service life.Polyimides is viscous
After the electrode of knot agent preparation recycles 100 times under the current density of 0.5C, specific discharge capacity still has 134.1mAh g-1, capacity
Conservation rate is 94.11%, and the electrode discharge specific capacity of PVDF binder preparation and capacity retention ratio are respectively 93.3mAh g-1、
76.67%.Meanwhile electrode discharge specific capacity prepared by polyimide binder is 84.8mAh g under the current density of 2C-1,
And the electrode of PVDF binder preparation only has 68.8mAh g-1, and the current density of 0.1C is filled after the completion of 2C charge and discharge
It discharges, electrode capacity retention ratio with higher prepared by polyimide binder.
Detailed description of the invention
Fig. 1 is in the embodiment of the present invention 1 containing bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 4,4'- diamino
Diphenyl sulphone (DPS) and 3,3 ', the infrared figure of polyimides synthesized by 4,4 '-benzophenone tetracarboxylic dianhydrides；
Fig. 2 is in the embodiment of the present invention 1 containing bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 4,4'- diamino
Diphenyl sulphone (DPS) and 3,3 ', polyimides and PVDF synthesized by 4,4 '-benzophenone tetracarboxylic dianhydrides are the positive pole of binder
Piece, lithium piece are the AC impedance curve of the button half-cell of cathode preparation at room temperature；
Fig. 3 is in the embodiment of the present invention 1 containing bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 4,4'- diamino
Diphenyl sulphone (DPS) and 3,3 ', polyimides and PVDF synthesized by 4,4 '-benzophenone tetracarboxylic dianhydrides are the positive pole of binder
Piece, lithium piece are that the 5V of the button half-cell of cathode preparation at room temperature overcharges curve；
Fig. 4 is in the embodiment of the present invention 1 containing bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 4,4'- diamino
Diphenyl sulphone (DPS) and 3,3 ', polyimides and PVDF synthesized by 4,4 '-benzophenone tetracarboxylic dianhydrides are the positive pole of binder
Piece, lithium piece are the high rate performance curve of the button half-cell of cathode preparation at room temperature；
Fig. 5 is in the embodiment of the present invention 1 containing bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4-, 4,4'- diamino
Diphenyl sulphone (DPS) and 3,3 ', polyimides and PVDF synthesized by 4,4 '-benzophenone tetracarboxylic dianhydrides are the positive pole of binder
Piece, lithium piece are the cycle performance curve of the button half-cell of cathode preparation at room temperature.
Specific embodiment
The present invention will be described in further detail below with reference to the embodiments of the drawings, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1
In the present embodiment, lithium ion cell positive binder is polyimide polymer, structural formula are as follows:
Wherein, the m:n=3:1 in synthesized polyimides.
Above-mentioned binder the preparation method comprises the following steps: by the bis- (2- trifluoromethyl -4- aminobenzene oxygen of the 1,4- of 10mmol diamine monomer
Base) benzene, 4,4'- diaminodiphenylsulfone be dissolved in 40mL metacresol, and stirring makes it be added solvent 0.3vol%'s after completely dissolution
3,3', 4,4'- benzophenone tetracarboxylic dianhydride of catalyst isoquinolin and 10mmol dianhydride monomer, is discharged by stream of nitrogen gas band
Point, stir 4h at room temperature, after be warming up to 180 DEG C of dehydration imidizate 6h, reactant is poured into ethyl alcohol after cooling, is obtained
Fibrous white or light yellow polyimide polymer, are denoted as 6FAPB/DDS-BTDA.
Fig. 1 is the infrared figure of 6FAPB/DDS-BTDA synthesized in embodiment 1, tests used Fourier transform infrared
Spectrometer model VECTOR33 (Bruker, Germany), sample test condition: directly uses pressing potassium bromide troche, under high temperature sodium vapor lamp
Drying, scanning range 3500-600cm-1.By designed polyimide structures formula it is found that synthetic mainly contains C=O, C-
N、-SO2-、-CF3And the groups such as-O-.Wherein, in 1782cm in the infrared figure of Fig. 1-1And 1723cm-1The absorption peak at place belongs to C=
The asymmetric vibration of O and symmetric vibration peak, 1436cm-1And 718cm-1The absorption peak at place belongs to C-N key and C- in polyimides ring
The asymmetric vibration peak of N-C, and-SO2Asymmetric stretching vibration and symmetrical flexible symmetrical respectively in 1320cm-1And 1129cm-1, 1370cm-1The absorption peak at place belongs to-CF3Stretching vibration, the asymmetric stretching vibration of-O- and symmetrical flexible symmetrical right respectively
It should be in the characteristic peak at the 1233cm-1 and 1049cm-1 in infrared figure.In conclusion illustrating designed in embodiment 1
6FAPB/DDS-BTDA is synthesized successfully.
When using the lithium ion cell positive that 6FAPB/DDS-BTDA is prepared as binder, the binder polymer side chain unit
In-the SO that contains2There is strong electron attraction and hygroscopicity, enhancing electrode and lithium ion binding ability, and improve electrode to electricity
The absorption of liquid is solved, electrode impedance is reduced；- the CF contained3Enhance ion transferring capability, electrochemical stability, thermal stability with
And solvability in organic solvent；The caking property and flexibility of the-CO- contained and-O- enhancing polyimides, ensure that lithium
The cyclical stability and overcharge safety of ion battery.
Anode slice of lithium ion battery is prepared using 6FAPB/DDS-BTDA, which collected using aluminium foil as collector
Flow surface coats active material layer, and active material layer is with LiFePO4Powder is positive active material, and acetylene black is as conductive
Agent and above-mentioned 6FAPB/DDS-BTDA are as binder.
Anode slice of lithium ion battery preparation method and battery assembly method are as follows:
It takes the 6FAPB/DDS-BTDA of 0.5g to be dissolved in the N-Methyl pyrrolidone of 20mL, obtains binder solution；Take 4g
LiFePO4After positive active material powder, 0.5g acetylene black are fully ground mixing, it is added portionwise in binder solution, and stir
Mixing is uniformly mixed it, obtains active material slurry；After the active material slurry ultrasound deaeration, it is uniformly coated on aluminium foil
On, 80 DEG C of vacuum dryings after being compacted using tablet press machine, obtain LiFePO4Anode pole piece.
The assembly of battery mainly carries out in glove box, and oxygen and moisture content are both less than 5ppm in glove box, selected
Battery case be CR2025 type, diaphragm be Celgard2500 PP diaphragm, the electrolysis liquid hold-up of each battery is about 80 μ L.Its
In, the assembling sequence of battery is anode cover | positive plate | electrolyte | and diaphragm | electrolyte | lithium piece | nickel foam | negative electrode casing.
Comparative example 1
In this comparative example, the binder that lithium ion cell positive uses is PVDF (HSV900, A Kema, France).
It is identical as other positive electrodes in above-described embodiment 1 using the lithium ion battery of above-mentioned binder, it prepares and assembles and implement
Preparation method in example 1 is identical.
It takes the PVDF binder of 0.5g to be dissolved in the N-Methyl pyrrolidone of 20mL, obtains binder solution；It takes
4gLiFePO4After positive active material powder, 0.5g acetylene black are fully ground mixing, it is added portionwise in binder solution, and stir
Mixing is uniformly mixed it, obtains active material slurry；After the active material slurry ultrasound deaeration, it is uniformly coated on aluminium foil
On, 80 DEG C of vacuum dryings after being compacted using tablet press machine, obtain LiFePO4Anode pole piece.
Fig. 2 is that above-described embodiment 1 with the battery that anode pole piece prepared by comparative example 1 is assembled exchanges resistance at room temperature
Anti- test result, is tested used electrochemical workstation model CHI660D (Hua Chen, China), battery testing condition: amplitude is
1mV, frequency range 1-100kHz.Wherein, figure middle line 1 is binder is 6FAPB/DDS-BTDA in embodiment 1 circulation 3 times
Rear ac impedance measurement is as a result, AC impedance after figure middle line 2 be that binder is PVDF in comparative example 1 circulation 3 times
Test result, figure middle line 3 are the ac impedance measurement after circulation 100 times that binder is 6FAPB/DDS-BTDA in embodiment 1
As a result, the ac impedance measurement result after figure middle line 4 be that binder is PVDF in comparative example 1 circulation 100 times.From figure
It is observed that after prepared electrode cycle 3 times form corresponding SEI film, the preparation of 6FAPB/DDS-BTDA binder
Electrode has the smallest 30 Ω of impedance value, and its impedance value of electrode of commercialized PVDF binder preparation is 88 Ω, illustrates it
With preferable electric conductivity, reason may be due to-SO2Strong electron attraction and-CF3Presence, improve electronics
Migration rate, to reduce electrode impedance value.After recycling 100 times, the irreversible reaction of electrolyte increases, and in electrode
Portion's structure becomes lawsuit, so that the AC impedance of electrode be made to become larger.Electrode 100 times of 6FAPB/DDS-BTDA binder preparation
Impedance value is 141 Ω after circulation, and the impedance value of the electrode of PVDF binder preparation then has 205 Ω, reason may be due to-
The presence of CO- increases the viscosity of binder, thus make synthesized 6FAPB/DDS-BTDA that there is better cementitiousness, from
And each component in electrode is made to bond even closer, the volume change being suitable in charge and discharge process.
Fig. 3 is that 5V overcharges survey to the battery that is assembled of anode pole piece prepared by the present embodiment 1 and comparative example 1 at room temperature
Test result, blue electric battery test system model CT2001A (LAND, China), battery testing condition: electric current used by testing
Density is 0.1C, voltage range 2.5-3.8V.Wherein, figure middle line 2 is that binder is 6FAPB/DDS-BTDA's in embodiment 1
Test result, figure middle line 1 are the test result that binder is PVDF in comparative example 1.It can be seen from the figure that initial
In 3 circulations, the charge and discharge process of battery is almost the same.When preparing electrode using PVDF binder, stage battery is overcharged
Charging voltage drop directly rises to 5V.And when making binder using 6FAPB/DDS-BTDA, the rising of voltage during overcharging
Process will slow down.The electrode of PVDF, 6FAPB/DDS-BTDA binder preparation crosses the difference of time used by being charged to 5V from 2.5V
For 13.6h, 29.3h, the electrode of 6FAPB/DDS-BTDA binder preparation overcharges that duration is longer, illustrates that it is overcharged with excellent
Security performance, reason may be that 6FAPB/DDS-BTDA has preferable mechanical performance, can effectively alleviate electrode structure
Destruction, and contain-CO- and-SO in prepared 6FAPB/DDS-BTDA structure2, increase binder conjugated structure
Stability, make its electrode each section bonding it is even closer.Meanwhile 6FAPB/DDS-BTDA I has preferable thermal stability,
It, which makees binder, can effectively improve the hot property of electrode, to be effectively improved the exothermic phenomenon during it is overcharged, slow down process
In kinetic reaction, and then improve overcharge safety energy.
Fig. 4 is the battery that is assembled of anode pole piece prepared by the present embodiment 1 and comparative example 1 high rate performance at room temperature
Test result, blue electric battery test system model CT2001A (LAND, China), battery testing condition: electricity used by testing
Current density is 0.1C, 0.2C, 0.5C, 1C and 2C, voltage range 2.5-3.8V.Wherein, in figure 2 to bond in embodiment 1
Agent is the test result of 6FAPB/DDS-BTDA, and figure middle line 1 is the test result that binder is PVDF in comparative example 1.By
For figure it is found that compared to PVDF, the electrode of 6FAPB/DDS-BTDA binder preparation has highest specific discharge capacity at 0.1C
164.1mAh g-1, reason may be due to-SO2And-CF3Presence enhance the compatibility of electrode and electrolyte, thus
Accelerate Ion transfer speed, and then improves its chemical property, and-SO2There is stronger hygroscopicity, further change
Electrolyte has been apt to it to the wellability of electrode.Electrode discharge specific capacity prepared by polyimide binder is under the current density of 2C
84.8mAh g-1, and the electrode of PVDF binder preparation only has 68.8mAh g-1, after the completion of 2C charge and discharge, return to 0.1C's
Current density carries out charge and discharge it can be found that the electrode of 6FAPB-BTDA, 6FAPB/DDS-BTDA binder preparation is with higher
Capacity retention ratio, illustrate its charge and discharge being suitable under high current density, possible cause is-SO2Presence enhance
The stabilization of polyimide binder conjugated system so that electrode structure stability be enable to be promoted, and then increases battery not
With the stability of charge and discharge under current density.
Fig. 5 is the battery that is assembled of anode pole piece prepared by the present embodiment 1 and comparative example 1 cycle performance at room temperature
Test result is surveyed, blue electric battery test system model CT2001A (LAND, China), battery testing condition: electricity used by trying
Current density is 0.5C, voltage range 2.5-3.8V.Wherein, line 2 is the survey that binder is 6FAPB/DDS-BTDA in embodiment 1
Test result, line 1 are the test result that binder is PVDF in comparative example 1.As seen from the figure, the current density of initial 0.1C
Under 3 circulations in, battery be in the state of activation, and electrolyte is gradually immersed into electrode interior, therefore in the appearance by a small margin of its capacity
The phenomenon that rising.And in the charge and discharge process under 0.5C temperature current density behind, battery capacity is gradually reduced, and is followed for 100 times
After ring, the specific discharge capacity of the electrode of PVDF, 6FAPB/DDS-BTDA binder preparation is respectively 93.3mAh g-1、134.1mAh
g-1, it is 76.67%, 94.11% with respect to the capacity retention ratio recycled for the first time under 0.5C, illustrates 6FAPB/DDS-BTDA binder system
Standby electrode has preferable cyclical stability, and reason may be because of-SO2Presence, increase electrolyte and electrode phase
Capacitive, so that electrolyte be made to be more easier to penetrate into electrode.For PVDF, 6FAPB-BTDA, 6FAPB/DDS-BTDA bonding
The electrode cycle performance of agent preparation is more preferably, it may be possible to which-the CO- as contained in its molecular structure enhances its caking property, makes
Each component bonding is stronger in electrode, not only forms corresponding conductive network, but also make the construction of electrode interior material more
Add stabilization, and due to-SO2The stability of polyimides conjugated system is enhanced, to make the long-term stable charge/discharge of battery
It is promoted.
Embodiment 2
In the present embodiment, lithium ion cell positive binder is polyimide polymer, structural formula are as follows:
Wherein, the m:n=3:1 in synthesized polyimides.
Above-mentioned binder the preparation method comprises the following steps: by the bis- (2- trifluoromethyl -4- aminobenzoyls of 15mmol diamine monomer 1,4-
Base) benzene, 4,4'- diaminodiphenyl ether be dissolved in 70mL parachlorphenol, and stirring makes it be added solvent 0.4vol%'s after completely dissolution
3,3', 4,4'- diphenylsulfone acid's dianhydride of catalyst quinoline and 15mmol dianhydride monomer, takes moisture, room out of by stream of nitrogen gas
Temperature is lower to stir 5h, after be warming up to 190 DEG C of dehydration imidizate 8h, reactant is poured into methanol after cooling, obtains fiber
Shape white or light yellow polyimide polymer.
Anode slice of lithium ion battery is prepared using the binder, which is using aluminium foil as collector, in afflux body surface
Face coats active material layer, and active material layer is with LiFePO4Powder is positive active material, acetylene black as conductive agent, with
And above-mentioned polyimide polymer is as binder.
Above-mentioned anode slice of lithium ion battery preparation method and battery assembly method are as follows:
It takes the 0.5g binder to be dissolved in 20mLN- methyl pyrrolidone, obtains binder solution；Take 4gLiFePO4Anode
It after active material powder, 0.5g acetylene black are fully ground mixing, is added portionwise in binder solution, and stirring keeps its mixing equal
It is even, obtain active material slurry；It after the active material slurry ultrasound deaeration, is uniformly coated on aluminium foil, 80 DEG C of vacuum are dried
It is dry, after being compacted using tablet press machine, obtain LiFePO4Anode pole piece.
The assembly of battery mainly carries out in glove box, and oxygen and moisture content are both less than 5ppm in glove box, selected
Battery case be CR2025 type, diaphragm be Celgard2500 PP diaphragm, the electrolysis liquid hold-up of each battery is about 80 μ L.Its
In, the assembling sequence of battery is anode cover | positive plate | electrolyte | and diaphragm | electrolyte | lithium piece | nickel foam | negative electrode casing.
Embodiment 3
In the present embodiment, lithium ion cell positive binder is polyimide polymer, structural formula are as follows:
Wherein, the m:n=3:1 in synthesized polyimides.
Binder the preparation method comprises the following steps: by bis- (2- trifluoromethyl -4- aminobenzene sulfuryl) benzene of 20mmol diamine monomer 1,4-,
4,4'- diaminodiphenyl ethers are dissolved in 80mL m-Chlorophenol, and stirring makes it that the catalyst of solvent 0.3vol% be added after completely dissolution
3,3', 4,4'- benzophenone tetracarboxylic dianhydride of tertiary amine and 20mmol dianhydride monomer, takes moisture out of by stream of nitrogen gas, at room temperature
Stir 8h, after be warming up to 200 DEG C of dehydration imidizate 10h, reactant is poured into ethyl alcohol after cooling, is obtained fibrous white
Color or light yellow polyimide polymer.
Anode slice of lithium ion battery is prepared using the binder, which is using aluminium foil as collector, in afflux body surface
Face coats active material layer, and active material layer is with LiFePO4Powder is positive active material, acetylene black as conductive agent, with
And above-mentioned polyimide polymer is as binder.
Above-mentioned anode slice of lithium ion battery preparation method and battery assembly method are as follows:
It takes the 0.5g binder to be dissolved in 20mLN- methyl pyrrolidone, obtains binder solution；Take 4gLiFePO4Anode
It after active material powder, 0.5g acetylene black are fully ground mixing, is added portionwise in binder solution, and stirring keeps its mixing equal
It is even, obtain active material slurry；It after the active material slurry ultrasound deaeration, is uniformly coated on aluminium foil, 80 DEG C of vacuum are dried
It is dry, after being compacted using tablet press machine, obtain LiFePO4Anode pole piece.
The assembly of battery mainly carries out in glove box, and oxygen and moisture content are both less than 5ppm in glove box, selected
Battery case be CR2025 type, diaphragm be Celgard2500 PP diaphragm, the electrolysis liquid hold-up of each battery is about 80 μ L.Its
In, the assembling sequence of battery is anode cover | positive plate | electrolyte | and diaphragm | electrolyte | lithium piece | nickel foam | negative electrode casing.
Embodiment 4
In the present embodiment, lithium ion cell positive binder is polyimide polymer, structural formula are as follows:
Wherein, m:n=5:1~1:5 in synthesized polyimides.
Lithium ion cell positive binder the preparation method comprises the following steps: by the bis- (2- trifluoromethyl -4- of 25mmol diamine monomer 1,4-
Aminobenzene sulfuryl) benzene, 4,4'- diaminobenzophenone be dissolved in 120mL metacresol, and stirring makes it that solvent be added after completely dissolution
The catalyst quinoline and 25mmol dianhydride monomer 4 of 0.5vol%, 4'- biphenyl ether dianhydride take moisture, room temperature out of by stream of nitrogen gas
Lower stirring 10h, after be warming up to 210 DEG C of dehydration imidizate 12h, reactant is poured into methanol after cooling, obtains fiber
Shape white or light yellow polyimide polymer.
Anode slice of lithium ion battery is prepared using the binder, which is using aluminium foil as collector, in afflux body surface
Face coats active material layer, and active material layer is with LiFePO4Powder is positive active material, acetylene black as conductive agent, with
And above-mentioned polyimide polymer is as binder.
Above-mentioned anode slice of lithium ion battery preparation method and battery assembly method are as follows:
It takes the 0.5g binder to be dissolved in 20mLN- methyl pyrrolidone, obtains binder solution；Take 4gLiFePO4Anode
It after active material powder, 0.5g acetylene black are fully ground mixing, is added portionwise in binder solution, and stirring keeps its mixing equal
It is even, obtain active material slurry；It after the active material slurry ultrasound deaeration, is uniformly coated on aluminium foil, 80 DEG C of vacuum are dried
It is dry, after being compacted using tablet press machine, obtain LiFePO4Anode pole piece.
The assembly of battery mainly carries out in glove box, and oxygen and moisture content are both less than 5ppm in glove box, selected
Battery case be CR2025 type, diaphragm be Celgard2500 PP diaphragm, the electrolysis liquid hold-up of each battery is about 80 μ L.Its
In, the assembling sequence of battery is anode cover | positive plate | electrolyte | and diaphragm | electrolyte | lithium piece | nickel foam | negative electrode casing.
Electrochemical property test:
AC impedance, cycle performance, high rate performance and 5V is carried out to the battery assembled in above-described embodiment 2-4 to overcharge
Performance test, instrument and method used by testing are consistent with the instrument and method that embodiment 1 and comparative example use.
Table 1 is the comparison side test result data of embodiment 1-4 and comparative example.
Table 1
According to the test result of AC impedance shown in table 1 it is found that the battery of embodiment 1-4 is after circulation 3 times, impedance
Value is 30-35 Ω, and the impedance value of comparative example is then up to 88 Ω.After circulation 100 times, the impedance value of the battery of embodiment 1-4 is
141-156 Ω, the impedance value of comparative example are 205 Ω.The test result of embodiment 1-4 is better than comparative example, this illustrates positive use
After prepared polyimide binder, resistance is smaller, and electrolyte and electrode compatibility are preferable, is conducive to the multiplying power for improving battery
Performance.
The test result of test is overcharged according to 5V shown in table 1 it is found that the battery of embodiment 1-4 is crossed from 2.5V and is charged to 5V,
The used time is 29.3-30.1h, and the time used by comparative example is only 13.6h.The test result of embodiment 1-4
Better than comparative example, this illustrates anode using after prepared polyimide binder, and the time that overcharges of electrode is increased, and overcharges
Safety can be promoted.
According to the test result of high rate performance shown in table 1 it is found that the battery of embodiment 1-4 is under the current density of 2C
Specific discharge capacity value is 84.3-86.1mAh g-1, specific discharge capacity value of the comparative example under the current density of 2C is 68.8mAh
g-1, illustrate that the electrode of polyimide binder preparation has better high rate performance, the charge and discharge being suitable under high current density
Electricity, this is corresponding with the ac impedance measurement of front.
According to the test result of cycle performance shown in table 1 it is found that the battery of embodiment 1-4 is under the current density of 0.5C
Specific discharge capacity value be 132.7-134.3mAh g-1, specific discharge capacity value of the comparative example under the current density of 0.5C be
93.3mAh g-1, and applying capacity retention ratio of the battery of a 1-4 under the current density of 0.5C is 93.24-94.37%, and
Comparative example only has 76.67%, illustrates that the electrode of polyimide binder preparation has better cycle performance, the circulation of battery
Stability enhances the service life of battery.
It should be noted that the present invention is not limited to the above embodiments, before not departing from spirit and scope of the invention
It puts, various changes and improvements may be made to the invention, these changes and improvements both fall within claimed invention protection scope
It is interior；The claimed scope of the invention is defined by tbe claims.
Claims (10)
1. a kind of lithium ion cell positive binder, it is characterised in that: the binder is to contain-SO2-、-CF3,-CO- and-
The polyimide polymer of O-, structural formula such as following formula (1):
Wherein, m:n=5:1~1:5 in the polyimides；Degree of polymerization m+n is the integer of 100-5000；
The R1、R2And R3Structural formula be as follows:
Wherein, R1、R2、R3Structure by selection, so that the positive electrode binder is contained-SO simultaneously2-、-CF3,-CO- and-O-
Four kinds of groups.
2. the preparation method of lithium ion cell positive binder described in claim 1, it is characterised in that: diamine monomer to be dissolved in
In solvent, stirring takes moisture out of by stream of nitrogen gas, stirs 4 at room temperature to catalyst and dianhydride monomer are added after completely dissolution
~10h, heating dehydration imidizate, pours into reactant in methanol or ethyl alcohol after cooling, and obtains fibrous white or shallow
Yellow polyimide polymer；
The diamine monomer be 4,4'- diaminobenzophenone, 4,4'- diaminodiphenyl ether, 4,4' diaminodiphenyl sulfone,
2,2'- bis trifluoromethyl -4,4'- diamino hexichol, 1,4- bis- (2- trifluoromethyl -4- amino benzoyl) benzene, the bis- (2- of 1,4-
Trifluoromethyl -4- aminobenzene sulfuryl) one of benzene and bis- (2- trifluoromethyl-4-aminophenoxyl) benzene of 1,4- or a variety of；
The dianhydride monomer is 3,3',4,4' benzophenone tetracarboxylic dianhydride, 4,4'- biphenyl ether dianhydride, 3,3', 4,4'- bis-
Phenylsulfone tetracarboxylic dianhydride, 2,2'- bis trifluoromethyl -3,3', 4,4'- diphenyl ether tetraformic dianhydride, bis- (the 2- fluoroforms of 1,4-
Base -3,3',4,4' benzophenone tetracarboxylic dianhydride) benzene, bis- (2- trifluoromethyl -3,3', 4,4'- the diphenyl sulfone tetrabasic carboxylic acids of 1,4-
Dianhydride) one of benzene and bis- (2- trifluoromethyl -4,4'- biphenyl ether dianhydride) benzene of 1,4- or a variety of；
The solvent is metacresol, m-Chlorophenol or parachlorphenol；
The catalyst is quinoline, isoquinolin or tertiary amine.
3. the preparation method of lithium ion cell positive binder according to claim 2, it is characterised in that: described two
The molar ratio of amine monomers and dianhydride monomer is 1:1~1:1.02.
4. the preparation method of lithium ion cell positive binder according to claim 2, it is characterised in that: described urges
Agent accounts for the 0.2~0.5% of solvent volume；The solid content of diamines and dianhydride is in solution after catalyst and dianhydride monomer is added
5%~20%.
5. the preparation method of lithium ion cell positive binder according to claim 2, it is characterised in that: the liter
The temperature of temperature dehydration imidizate is 170~210 DEG C, and the time of heating dehydration imidizate is 5~20h.
6. a kind of lithium ion cell positive prepared using binder described in claim 1, it is characterised in that: the anode packet
Current collector aluminum foil and the active material layer coated in the current collector aluminum foil surface are included, the active material layer includes that anode is living
Property substance, conductive agent and the binder；The positive active material content is 2mg cm-2~4mg cm-2；The work
Property material layer in binder mass content be 1%~15%；In the active material layer conductive agent mass content be 3%~
20%.
7. lithium ion cell positive according to claim 7, it is characterised in that: the positive active material is ferric phosphate
One of lithium, cobalt acid lithium, LiMn2O4, lithium nickelate and tertiary cathode material nickle cobalt lithium manganate or a variety of kinds.
8. lithium ion cell positive according to claim 7, it is characterised in that: the conductive agent is acetylene black, superconduction
Carbon black, carbon nanotube, graphene with one of Ketjen black or a variety of.
9. according to the preparation method of the described in any item lithium ion cell positives of claim 6-8, it is characterised in that including as follows
Step:
1) it takes binder heating stirring to be dissolved in solvent, obtains binder solution；Take the powder and conductive agent of positive active material
Ground and mixed is uniformly added in binder solution afterwards, and the viscosity by adding solvent adjustment compounding substances is 2000~10000mpa
S obtains active material slurry；The solvent is N,N-dimethylformamide, N, N- dimethyl second formamide or N- methyl pyrrole
Pyrrolidone；
2) active material slurry is coated uniformly on aluminium foil, is compacted after dry, obtains lithium ion cell positive.
10. the preparation method of lithium ion cell positive according to claim 9, it is characterised in that: glued described in step 1)
The mass concentration for tying solution is 20%~40%；The drying is 60 DEG C~120 DEG C vacuum dryings.
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