CN105713198A - Polyimide, lithium ion battery as well as preparation method and application of lithium ion battery - Google Patents
Polyimide, lithium ion battery as well as preparation method and application of lithium ion battery Download PDFInfo
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- CN105713198A CN105713198A CN201610289109.0A CN201610289109A CN105713198A CN 105713198 A CN105713198 A CN 105713198A CN 201610289109 A CN201610289109 A CN 201610289109A CN 105713198 A CN105713198 A CN 105713198A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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
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- 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
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- 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
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Abstract
The invention discloses polyimide, a lithium ion battery as well as a preparation method and application of the lithium ion battery. The structure of the polyimide is as shown in the formula I in the specification, and the number-average molecular weight of the polyimide is 100000-140000. The polyimide disclosed by the invention is used as a lithium ion battery adhesive, and defects that conventional polyimide is poor in wettability and large in impedance to electrolyte, particularly under a condition of high-current density power charge and discharge, a conventional lithium ion battery which adopts polyimide as the adhesive is poor in rate capability and cycle performance and the like can be overcome. The polyimide disclosed by the invention is relatively good in wettability to electrolyte and can be used as the lithium ion battery adhesive; and with the combination of a polyimide diaphragm, a prepared lithium ion battery is low in impedance, good in rate capability and good in cycle performance.
Description
Technical field
The present invention relates to a kind of polyimides, lithium ion battery and its preparation method and application.
Background technology
In recent years, lithium ion battery has significantly high energy density because of it and outstanding cycle performance causes people and more and more pays close attention to.Along with its application is from small-sized electronic product, as: mobile phone, notebook computer and digital camera etc., it is gradually extended to large-sized battery field, as: electric automobile and hybrid power electric car etc., lithium ion battery requirement in circulation retention rate, energy density and security performance etc. also steps up.
Binding agent is ingredient critically important in lithium ion battery, and the performance of battery can be had a huge impact by its performance.Kynoar (PVDF), because a kind of having good adhesive property, electrolyte absorbability, chemistry and electrochemical stability, becomes current most widely used lithium ion battery binding agent.But, its fusing point is relatively low, and this causes that its heat stability is poor, can cause a series of safety problem.Meanwhile, when it dissolves in the non-aqueous electrolyte, forming a kind of fluid having certain viscosity or polymer gel, this can make electrode particle be peeling, and reduces high rate performance and the cycle life of battery.Polyimides (PI) has good mechanical performance, chemical stability and extremely low dielectric constant, particularly supereminent heat stability because of it, is applied to a lot of field.
Recent years, have been reported that and show that polyimides is compared to conventional binders, be a kind of more outstanding lithium ion battery binding agent.Ohta et al. find polyimides can be effectively improved can the reversibility of charging-discharging lithium ion battery, and the capacity of battery can along with in carbonyl in monomeric unit the increase of oxygen atom quantity and increase.Choi et al. finds after being incorporated into by polyimides in carbon binding agent, and battery cyclical stability under 60 DEG C of conditions obtains and improves largely.Kim et al. uses Kynoar and polyimides as binding agent assembled battery respectively, finding after the chemical property of both contrasts, polyimide binder can suppress silicon electrode due to the embedding of lithium ion and deviate from the physical expansion caused in electrochemical reaction process effectively.Polyimide binder is applied to graphite-silicon/oxidative silicon/carbon composite electrode by the team at Yuan place, and the result of their experiment shows that this electrode circulation retention rate after 30 circulations is greatly enhanced.In addition, combination electrode presents supereminent mechanical performance.
But, at present, polyimides and polyalkene diaphragm is adopted to be assembled the lithium ion battery obtained, its battery harmony is poor, and the internal resistance of battery is relatively big, and this makes the high rate performance of battery and cycle performance be severely impacted, when particularly in high current density discharge and recharge, and when long-term loop test, the high rate performance of lithium ion battery and cycle performance are not good.
Summary of the invention
After the technical problem to be solved is in that overcoming existing polyimides uses as binding agent, electrolyte wettability is poor, impedance is big, particularly when high current density discharge and recharge, adopt at present polyimides as not good etc. the defect of the high rate performance of the lithium ion battery of binding agent and cycle performance, a kind of polyimides and its preparation method and application is provided, and a kind of adopts this polyimides as lithium ion battery of binding agent and its preparation method and application.The polyimides of the present invention is better to the wettability of electrolyte, uses as lithium ion battery binding agent, coordinates polyimide diaphragm, and battery impedance is less, and obtained lithium ion battery good rate capability, cycle performance is good.
The present invention adopts following technical proposals to solve above-mentioned technical problem.
The invention provides a kind of polyimides, its structure shown in formula I:
Wherein, the number-average molecular weight of described polyimides is 100,000～140,000.
The preparation method that the invention provides a kind of described polyimides, it comprises the steps:
By 1; double; two (the 2-trifluoromethyl 4-amino-benzene oxygen) benzene (also known as 6FAPB) of 4-, 4; after 4 '-diaminodiphenyl ether (also known as ODA) and polar solvent mix homogeneously; add 3; 3 '; 4,4 '-diphenylsulfone acid dianhydride (also known as DSDA), to mixed dissolution, is subsequently adding catalyst and aromatic hydrocarbon solvent; under inert atmosphere protection; under room temperature and stirring, carry out polycondensation reaction, after polycondensation reaction, be warming up to 110.6～203 DEG C, carry out dehydration; dehydration cools down after terminating; after reacting, solution mixes with consolidation liquid, after drying, to obtain final product；
Wherein, described Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene, 4,4 '-diaminodiphenyl ether and 3,3 ', 4, the mol ratio of 4 '-diphenylsulfone acid dianhydride is 1:1:(2～2.04).
Wherein, described polar solvent can be polar solvent commonly used in the art, as long as being completely dissolved 6FAPB and ODA.Described polar solvent is preferably METHYLPYRROLIDONE (also known as NMP), and the consumption of described METHYLPYRROLIDONE can be the conventional amount used of this area；It is preferred that the volume mass ratio of described METHYLPYRROLIDONE and Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene is at more than 16.25mL/g.
Wherein, described catalyst can be catalyst commonly used in the art, it is preferred that for isoquinolin.The consumption of described isoquinolin can be the conventional amount used of this area, and the mass ratio of described isoquinolin and Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene is preferably (0.1～0.2): 4.
Wherein, described aromatic hydrocarbon solvent can be aromatic hydrocarbon solvent commonly used in the art, it is preferred that for toluene and/or dimethylbenzene.The consumption of described aromatic hydrocarbon solvent can be the conventional amount used of this area, as long as described catalyst can be dissolved.The mass volume ratio of described catalyst and described aromatic hydrocarbon solvent is preferably (0.2～0.4) g/ (22.5～25) mL.
Wherein, described inert atmosphere is the inert atmosphere that this area is conventional, by this area general knowledge, as long as it does not react with each material, is generally nitrogen.
Wherein, described room temperature is the room temperature on the conventional meaning of this area, is generally 20～35 DEG C.
Wherein, the method for described stirring and condition are the conventional method in this area and condition.
Wherein, the temperature of described polycondensation reaction is preferably 175～190 DEG C, is more preferably 180 DEG C.The method of described polycondensation reaction and other conditions are method and the condition of this area routine.The time of described polycondensation reaction is preferably 8～12h.
Wherein, the method for described dehydration and condition are the conventional method in this area and condition.The time of described dehydration is preferably 10～12h.By this area general knowledge, described dehydration remains in and carries out under inert atmosphere protection.
Wherein, the method for described cooling and condition can be the conventional method in this area and condition.Described cooling is preferably natural cooling.The target temperature of described cooling is preferably 90～100 DEG C.
Wherein, described consolidation liquid refers to the liquid for solidifying liquid polyimides, as long as it can not dissolve polyimides.Described consolidation liquid is preferably ethanol.By this area general knowledge, the consumption of described consolidation liquid can be that this area is conventional, as long as can be fully cured by the polyimides in solution after reaction.
By this area general knowledge, after " after reacting, solution mixes with ethanol ", before " drying ", it is also possible to the operation being filtered, to filter ethanol.Wherein, described dry method and condition can be method and the condition of this area routine.Described drying preferably carries out in vacuum drying oven.Described dry temperature is preferably 120～160 DEG C.The described dry time is preferably 8～12h.
Present invention also offers a kind of polyimides prepared by above-mentioned preparation method.
Present invention also offers the application as binding agent in lithium ion battery of described polyimides.
Present invention also offers a kind of lithium ion battery, wherein binding agent is described polyimides, and barrier film is Kapton.
In the present invention, the type of described lithium ion battery is that this area is conventional, can be half-cell or full battery；Wherein, electrode material is the electrode material that this area is conventional, and electrolyte is the electrolyte that this area is conventional.
Wherein, described polyimide diaphragm can be the polyimide diaphragm that this area is conventional, it is preferred that for the polyimide diaphragm PI-60 that Jiangxi Xiancai Nano Fiber Technology Co., Ltd. produces, the thickness of this polyimide diaphragm PI-60 is preferably 40 μm.
Meeting on the basis of this area general knowledge, above-mentioned each optimum condition, can combination in any, obtain the preferred embodiments of the invention.
Agents useful for same of the present invention and raw material are all commercially.
The actively progressive effect of the present invention is in that:
The polyimides of the present invention uses as lithium ion battery binding agent, coordinates polyimide diaphragm, and the impedance of obtained lithium ion battery is low, good rate capability, and cycle performance is good.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the polyimides of embodiment 1.
Fig. 2 is the TGA curve of Kynoar in the polyimides of embodiment 1 and comparative example 1.
Fig. 3 be PVDF-PE, PI-PE and PI-PI half-cell under the electric current density of 0.05C, the charging and discharging curve of first lap when voltage range is 0.01-2V.
Fig. 4 is (a) PVDF-PE, (b) PI-PE, (c) PI-PI respectively is 0.01-2V in voltage range, is the charging curve within the scope of 0.05C-5C in electric current density；And the charging curve (d) that three kinds of different batteries are under 1C electric current density.
Fig. 5 is the multiplying power figure of three kinds of batteries of PVDF-PE, PI-PE and PI-PI.
Fig. 6 is the impedance spectrum of three kinds of batteries of PVDF-PE, PI-PE and PI-PI.
Fig. 7 is the capability retention after three kinds of batteries of PVDF-PE, PI-PE and PI-PI circulate at 200 times with the electric current density of 1C and coulombic efficiency figure.
Detailed description of the invention
Mode by the examples below further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
Table 1 major experimental raw material relevant information
Table 2 major experimental instrument relevant information
In following embodiment, Kapton used is the polyimide diaphragm PI-60 that Jiangxi Xiancai Nano Fiber Technology Co., Ltd. produces, and its thickness is 40 μm.
Embodiment 1
Weigh 8.0300g1, double; two (4-amino-2-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 3.7550g4, after 4 '-diaminodiphenyl ether (ODA), after adding there-necked flask along funnel place, adding the METHYLPYRROLIDONE (NMP) of 130mL, stirring is to being completely dissolved.It is subsequently added 13.4350g3,3 ', 4,4 '-diphenylsulfone acid dianhydride (DSDA), stirring does not have obvious solid to liquid.After adding complete and dissolving until solid, adding 0.4000g isoquinolin and 22.5ml toluene in there-necked flask, after above-mentioned reactant adds, replaced by little funnel water knockout drum, one end of water knockout drum connects condensing tube, and one end passes into wastewater disposal basin.Keep passing into N2, mechanical agitation, when at room temperature, reactant generation polycondensation reaction, reaction carries out 8h.
Holding means is constant, and the temperature of solution is increased to 180 DEG C, opens condensed water, continues maintenance and passes into N2, can there is dehydration in reactant, reaction carries out 10h.After completion of the reaction, reactant liquor is naturally cooled to 90 DEG C.
Solution after cooling is poured slowly in excessive ethanol, forms light grey fibrous solids.Put in 120 DEG C of vacuum drying ovens, after dry 8h, solid polyimides is taken out, puts in drying basin standby.
Embodiment 2
Joining in METHYLPYRROLIDONE by the polyimides obtained by active material (graphite), conductive agent (acetylene black) and embodiment 1 according to mass ratio 8:1:1, stirring forms the slurry of stable homogeneous.Being uniformly coated on collector (Copper Foil) with film applicator, under 80 DEG C of conditions, vacuum drying 8h, takes out after cooling, obtains working electrode.Working electrode is pressed into the disk of diameter 12mm, is used for assembling CR2016 type button half-cell.Lithium sheet is used as electrode and reference electrode, 1MLiPF6It is dissolved in the solution that volume ratio is the ethylene carbonate of 1:1:1, Ethyl methyl carbonate and dimethyl carbonate as electrolyte.Respectively with Kapton as barrier film.Being below in the glove box of 0.1ppm to carry out battery assembling at water oxygen content, obtained half-cell is denoted as PI-PI.
Embodiment 3
After weighing the ODA of 6FAPB and 3.7550g of 8.0300g, after adding there-necked flask along funnel place, adding the NMP of 140mL, stirring is to being completely dissolved.Being subsequently added the DSDA of 13.4350g, stirring does not have obvious solid to liquid.After adding complete and dissolving until solid, adding 0.2100g isoquinolin and 25ml dimethylbenzene in there-necked flask, after above-mentioned reactant adds, replaced by little funnel water knockout drum, one end of water knockout drum connects condensing tube, and one end passes into wastewater disposal basin.Keep passing into N2, mechanical agitation, when at room temperature, reactant generation polycondensation reaction, reaction carries out 12h.
Holding means is constant, and the temperature of solution is increased to 110.6 DEG C, opens condensed water, continues maintenance and passes into N2, can there is dehydration in reactant, reaction carries out 12h.After completion of the reaction, reactant liquor is naturally cooled to 100 DEG C.
Solution after cooling is poured slowly in excessive ethanol, forms light grey fibrous solids.Filter after removing ethanol, put in 160 DEG C of vacuum drying ovens, after dry 12h, solid polyimides is taken out,.
Prepare half-cell according to embodiment 2, differ only in electrolyte and adopt 1MLiPF6It is dissolved in the ethylene carbonate and methyl ethyl carbonate ester solution that volume ratio is 1:1 as electrolyte.
Embodiment 4
After weighing the ODA of 6FAPB and 3.7550g of 8.0300g, after adding there-necked flask along funnel place, adding the NMP of 130mL, stirring is to being completely dissolved.Being subsequently added the DSDA of 13.4350g, stirring does not have obvious solid to liquid.After adding complete and dissolving until solid, adding 0.3000g isoquinolin and 25ml toluene in there-necked flask, after above-mentioned reactant adds, replaced by little funnel water knockout drum, one end of water knockout drum connects condensing tube, and one end passes into wastewater disposal basin.Keep passing into N2, mechanical agitation, when at room temperature, reactant generation polycondensation reaction, reaction carries out 10h.
Holding means is constant, and the temperature of solution is increased to 203 DEG C, opens condensed water, continues maintenance and passes into N2, can there is dehydration in reactant, reaction carries out 10h.After completion of the reaction, reactant liquor is naturally cooled to 90 DEG C.
Solution after cooling is poured slowly in excessive ethanol, forms light grey fibrous solids.Put in 140 DEG C of vacuum drying ovens, after dry 10h, solid polyimides taken out,.
Prepare half-cell according to embodiment 2, differ only in electrolyte and adopt 1MLiPF6It is dissolved in the solution that volume ratio is the ethylene carbonate of 1:1:1, dimethyl carbonate and diethyl carbonate as electrolyte.
Comparative example 1
Preparing half-cell according to embodiment 2, differ only in employing Kynoar as binding agent, adopt porous polyethylene film as barrier film, obtained half-cell is denoted as PVDF-PE.
Comparative example 2
Preparing half-cell according to embodiment 2, differ only in the polyimides adopting embodiment 1 as binding agent, adopt porous polyethylene film as barrier film, obtained half-cell is denoted as PI-PE.
Comparative example 3
Half-cell is prepared according to embodiment 2, differing only in wherein polyimides as binding agent is according to document " Preparationofthermalstableporouspolyimidemembranesbyphas einversionprocessforlithium-ionbattery " (WangH, Wang, YangS, FanL.) preparing, obtained half-cell is denoted as control sample 3.
Effect example
(1) infrared analysis, molecular weight test and TGA analyze
The infrared spectrum of the polyimides that embodiment 1 obtains is as it is shown in figure 1, the characteristic peak of imide group is 1780cm-1、1730cm-1And 1380cm-1, respectively asymmetric and symmetrical C=O, asymmetric C-N.The characteristic absorption peak of the asymmetric and symmetrical S=O of sulfonyl is at 1320cm-1And 1150cm-1Place.It addition, the C-F stretching vibration of trifluoromethyl is at 1240cm-1Observe.At 3300～3500cm-1Spectral region in do not observe the characteristic absorption of N-H of amino, it means that the characteristic peak of this polymer is by complete imidizate.Infrared spectrum it is shown that the preparation method of embodiment 1 obtains polyimides.
Relative molecular mass (Mn) and distribution tests thereof are recorded by the PL-GPC50 type chromatograph of gel permeation of Anjelen Sci. & Tech. Inc.With N, dinethylformamide (DMF) makees solvent and dissolves PI, test condition is as follows: temperature is 50 DEG C, and standard specimen is styrene, and fixing is vinyl benzene mutually, mobile phase is DMF (10mmolLiBr), flow velocity 1.00ml/min, sample concentration 2mg/ml, injection rate 100.0 μ l, column length 300mm, internal diameter is 7.8mm.After testing, the number-average molecular weight of the polyimides of embodiment 1,3 and 4 respectively 140000,103000 and 123000.
The TGA that Fig. 2 is Kynoar (PVDF) used in the polyimides (PI) of embodiment 1 and comparative example 1 analyzes curve.It can be seen that PVDF and PI starts to decompose when 433.8 DEG C and 485.1 DEG C respectively.When mass loss is 10%, the temperature of the two sample is 468.4 DEG C and 544.55 DEG C.Additionally, PI still has 16.9% undecomposed when 800 DEG C, but PVDF is completely broken down.Therefore, PI is proved to better than PVDF heat stability, owing to the heterocyclic imide ring on main chain and the aromatic ring that combines on main chain/or side base cause.
(2) electro-chemical test
Fig. 3 be PVDF-PE, PI-PE and PI-PI half-cell under the electric current density of 0.05C, the charging and discharging curve of first lap when voltage range is 0.01-2V.These three battery charge and discharge process is stable.For using the battery of traditional PVDF binding agent and PE barrier film, charging capacity is only 368.94mAh/g.As a comparison, the charging capacity of PI-PE is 355.30mAh/g.This Capacity Ratio PVDF-PE is lower slightly, it may be possible to due to the low harmony of PI binding agent and PE barrier film.Additionally, the battery charge capacity using PI-PI is that 366.31mAh/g and PVDF-PE sample has similar capacity.In view of the theoretical capacity of graphite is 372mAh/g, the result of charging and discharging curve means to reach, at PI-PI, the specific capacity that comparison is high.The half-cell of embodiment 3, embodiment 4 and comparative example 3 is tested, and acquired results shows specific capacity respectively 345.45mAh/g and the 365.98mAh/g of embodiment 3 and 4, and the specific capacity of control sample 3 is 337.45mAh/g.
Fig. 4 (a-c) is (a) PVDF-PE, (b) PI-PE, (c) PI-PI respectively is 0.01-2V in voltage range, is the charging curve within the scope of 0.05C-5C in electric current density.In the drawings, all batteries have stable charging platform, and along with the increase of electric current density, capacity declines.Meanwhile, PI-PI battery has the capacity higher than other two Battery packs.As shown in Fig. 4 (d), much higher than PVDF-PE (87.52mAh/g) and higher PI-PE (214.02mAh/g) of the active volume (266.04mAh/g) of PI-PI.Capability retention respectively 72.6%, 23.7% and 60.2%.The half-cell of embodiment 3 and embodiment 4 is tested, and the capability retention of acquired results and PI-PI battery is suitable, and respectively 68.0%～72.8%；And the capability retention of control sample 3 is 63.8%.
As shown in Figure 5, it can be seen that at low discharge electric current (0.05 DEG C to 0.2 DEG C), they have similar capacity, and this is the theoretical capacity close to graphite.When electric current density is 0.5C to 2C, it can be observed that compared with other two Battery packs, the capacity of PVDF-PE battery is decreased obviously.This result can be explained by the appreciable impact of ion migration.The migration of PVDF-PE limiting lithium ion, causes the increase of internal resistance, and this can affect its high rate performance.It is emphasized that when energy density reaches 5C, the capacity of three curves all sharply declines.This behavior is that the electric polarization produced by the increase of electric current density is affected.At high current density, particularly in the scope of 0.5C-2C, the high rate performance of the battery of PI-PI is greatly improved compared with PVDF-PE and PI-PE.Additionally, the half-cell of embodiment 3, embodiment 4 and comparative example 3 is carried out above-mentioned test, acquired results shows that the high rate performance of control sample 3 is suitable with PVDF-PE battery, and the sample of embodiment 3 and embodiment 4 is suitable with the high rate performance of PI-PI battery.
Three batteries are done electrochemical impedance spectroscopy (EIS) test.Fig. 6 is the Nyquist curve that PVDF-PE, PI-PE and PI-PI sweep the battery of three circles under 0.05C electric current density, and the curve obtained all is made up of three parts: the intercept on transverse axis, bulk resistance on curve；At the semicircle of high-frequency region, reflect interface resistance；At the nearly straight line of 45 ° of low frequency region one, reflect the Wo Baige diffusion of lithium ion.Can clearly finding, no matter be bulk resistance or interface resistance, PI-PI is minimum in three samples, and PI-PE also than PVDF-PE low.The most low-resistance of PI-PI not only gives the credit to the hydrophilic sulfonyl in PI binding agent, due also to the good wettability of PI barrier film, this makes electrolyte readily permeable.Additionally, two-part combination can the affinity of intensifier electrode and efficiently reduce internal resistance.Therefore, the battery that PI binding agent and PI barrier film combine has good high rate performance, and its low resistance plays conclusive effect.
Except good high rate performance, cyclical stability has also functioned to vital effect for long-life lithium ion battery.In order to investigate cyclical stability, testing the battery with different binding agents and barrier film is the continuous discharge-charging cycle under 1C in electric current density.As it is shown in fig. 7, under PVDF-PE, PI-PE and PI-PI circulate at 200 times with the electric current density of 1C, the cycle performance of the battery of PI-PI is better, and capability retention is 86.42%.But based on the capability retention of PVDF-PE less than 60%, PI-PE is 66.85%.Showing good efficiency for charge-discharge in all three sample, the conservation rate after discharge and recharge 200 circle is all close to 90%, and this embodies the reversible charging and discharging capabilities that it is good.The better wettability of PI-PI and harmony can bring relatively low resistance, then make to lose less in embedding-deintercalation process in the process of lithium ion.As a result of which it is, use PI-PI battery can keep optimum state when continuous discharge and recharge.The half-cell of embodiment 3, embodiment 4 and comparative example 3 is carried out above-mentioned test, and result shows that the high rate performance of control sample 3 is suitable with PVDF-PE battery, and the sample of embodiment 3 and embodiment 4 is suitable with the cyclical stability of PI-PI battery.
Claims (10)
1. a polyimides, it is characterised in that its structure shown in formula I:
Wherein, the number-average molecular weight of described polyimides is 100,000～140,000.
2. the preparation method of a polyimides as claimed in claim 1, it is characterised in that it comprises the steps:
By Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene, 4,4 '-diaminodiphenyl ether and after polar solvent mix homogeneously; add 3,3 ', 4; 4 '-diphenylsulfone acid dianhydride, to mixed dissolution, is subsequently adding catalyst and aromatic hydrocarbon solvent, under inert atmosphere protection; under room temperature and stirring, carry out polycondensation reaction, after polycondensation reaction, be warming up to 110.6～203 DEG C, carry out dehydration; dehydration cools down after terminating; after reacting, solution mixes with consolidation liquid, after drying, to obtain final product；
Wherein, described Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene, 4,4 '-diaminodiphenyl ether and 3,3 ', 4, the mol ratio of 4 '-diphenylsulfone acid dianhydride is 1:1:(2～2.04).
3. preparation method as claimed in claim 2, it is characterised in that described polar solvent is METHYLPYRROLIDONE；
And/or, described catalyst is isoquinolin；
And/or, described aromatic hydrocarbon solvent is toluene and/or dimethylbenzene；
And/or, the mass volume ratio of described catalyst and described aromatic hydrocarbon solvent is (0.2～0.4) g/ (22.5～25) mL.
4. preparation method as claimed in claim 3, it is characterised in that the volume mass ratio of described METHYLPYRROLIDONE and Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene is at more than 16.25mL/g；
And/or, the mass ratio of described isoquinolin and Isosorbide-5-Nitrae-bis-(2-trifluoromethyl 4-amino-benzene oxygen) benzene is (0.1～0.2): 4.
5. preparation method as claimed in claim 2, it is characterised in that the temperature of described polycondensation reaction is 175～190 DEG C；The time of described polycondensation reaction is 8～12h；
And/or, the time of described dehydration is 10～12h；
And/or, described cooling is natural cooling, and the target temperature of described cooling is 90～100 DEG C；
And/or, described consolidation liquid is ethanol；
And/or, described drying carries out in vacuum drying oven；Described dry temperature is 120～160 DEG C；The described dry time is 8～12h.
6. the polyimides prepared by Claims 1 to 5 any one preparation method.
7. as described in claim 1 or 6 polyimides in lithium ion battery as the application of binding agent.
8. a lithium ion battery, it is characterised in that wherein binding agent is the polyimides as described in claim 1 or 6, barrier film is Kapton.
9. lithium ion battery as claimed in claim 8, it is characterised in that described polyimide diaphragm is polyimide diaphragm PI-60.
10. lithium ion battery as claimed in claim 9, it is characterised in that the thickness of this polyimide diaphragm PI-60 is 40 μm.
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Cited By (4)
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| CN107383404A (en) * | 2017-07-03 | 2017-11-24 | 西南科技大学 | A kind of preparation method of fluorine-containing branched sulphonated polyimides proton conductive membrane |
| CN108417837A (en) * | 2018-02-12 | 2018-08-17 | 吴艳飞 | A kind of aqueous polyimide adhesive of Anode of lithium cell material and preparation method |
| CN111777984A (en) * | 2020-06-17 | 2020-10-16 | 浙江中科玖源新材料有限公司 | Sulfonated polyimide binder, electrode plate and lithium ion battery |
| CN112635769A (en) * | 2020-12-22 | 2021-04-09 | 桂林电器科学研究院有限公司 | Binder for lithium ion battery negative electrode, preparation method thereof, negative electrode containing binder and lithium ion battery |
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| US20110123796A1 (en) * | 2009-11-20 | 2011-05-26 | E.I. Dupont De Nemours And Company | Interposer films useful in semiconductor packaging applications, and methods relating thereto |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383404A (en) * | 2017-07-03 | 2017-11-24 | 西南科技大学 | A kind of preparation method of fluorine-containing branched sulphonated polyimides proton conductive membrane |
| CN108417837A (en) * | 2018-02-12 | 2018-08-17 | 吴艳飞 | A kind of aqueous polyimide adhesive of Anode of lithium cell material and preparation method |
| CN111777984A (en) * | 2020-06-17 | 2020-10-16 | 浙江中科玖源新材料有限公司 | Sulfonated polyimide binder, electrode plate and lithium ion battery |
| CN111777984B (en) * | 2020-06-17 | 2022-05-20 | 浙江中科玖源新材料有限公司 | Sulfonated polyimide binder, electrode plate and lithium ion battery |
| CN112635769A (en) * | 2020-12-22 | 2021-04-09 | 桂林电器科学研究院有限公司 | Binder for lithium ion battery negative electrode, preparation method thereof, negative electrode containing binder and lithium ion battery |
| CN112635769B (en) * | 2020-12-22 | 2022-05-06 | 桂林电器科学研究院有限公司 | Binder for lithium ion battery negative electrode, preparation method thereof, negative electrode containing binder and lithium ion battery |
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| CN105713198B (en) | 2018-09-28 |
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