CN103840201A - P(VDF-HFP) (Polyvinylidene Fluoride-Hexafluoropropylene)-based gel polymer electrolyte membrane, and preparation method thereof and lithium ion battery - Google Patents
P(VDF-HFP) (Polyvinylidene Fluoride-Hexafluoropropylene)-based gel polymer electrolyte membrane, and preparation method thereof and lithium ion battery Download PDFInfo
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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Abstract
The invention relates to a preparation method of a P(VDF-HFP) (Polyvinylidene Fluoride-Hexafluoropropylene)-based gel polymer electrolyte membrane. The preparation method disclosed by the invention comprises the following steps: (a), preparing a P(VDF-HFP)-based gel polymer membrane; and (b), preparing the P(VDF-HFP)-based gel polymer electrolyte membrane. The invention further relates to a lithium ion battery formed by assembling the P(VDF-HFP)-based gel polymer electrolyte membrane. According to the invention, the electrical conductivity of the gel polymer electrolyte membrane can be effectively improved by forming pores in P(VDF-HFP); after the gel polymer electrolyte membrane is assembled into the lithium ion battery, the specific capacity of the lithium ion battery is also increased; furthermore, compared with commercial organic liquid electrolytes currently, the P(VDF-HFP)-based gel polymer electrolyte membrane prepared by the method disclosed by the invention has the better stability and safety.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to P (VDF-HFP) (Kynoar-hexafluoropropylene) base gel polymer electrolyte film and preparation method thereof.The invention still further relates to and adopt the prepared lithium ion battery of this P (VDF-HFP) base gel polymer electrolyte film.
Background technology
Lithium ion battery is the advantage such as volume is little, lightweight, high power capacity, memory-less effect owing to having, thereby is widely used in the fields such as mobile phone, mobile phone, military affairs and electric automobile.
Lithium-ion battery electrolytes is divided into organic liquid electrolyte and polymer dielectric.The advantage of now widely used liquid electrolyte is that conductivity is high, but inflammable owing to containing, volatile organic solvent, it discharges fuel gas in charge and discharge process, particularly under some unconventional condition of work, (discharge and recharge as high-power, super-charge super-discharge etc.) produces large calorimetric meeting and accelerates the generation of gas, cause inner pressure of battery to increase,, even to blast on fire, thereby there is serious potential safety hazard in Leakage Gas.Polymer electrolyte lithium-ion battery because thering is safety, without leaking, leakage current is little, can arbitrary shape etc. the studied person of advantage pay attention to.Under solid polymer electrolyte room temperature, conductivity is lower by (10
-5～10
-4s/cm), use application to be restricted, thereby gel polymer electrolyte (also claiming gel polymer electrolyte film) become research emphasis.
Summary of the invention
The object of the invention is to solve the problem and shortage that above-mentioned prior art exists, a kind of P (VDF-HFP) base gel polymer electrolyte film and preparation method thereof and the lithium ion battery that adopts this P (VDF-HFP) base gel polymer electrolyte film to assemble are provided.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: the preparation method of a kind of P (VDF-HFP) base gel polymer electrolyte film, comprises the steps.(a) prepare P (VDF-HFP) base gelatin polymer film: under inert gas shielding; P (VDF-HFP), organic solvent and pore creating material are stirred 10:30 ~ 50:1 ~ 2 in mass ratio; mix to obtain mucus; be cast in casting film-forming on barrier film, after vacuumize, obtain described P (VDF-HFP) base gelatin polymer film.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: 10～60min during dried described P (VDF-HFP) base gelatin polymer film is immersed in to lithium salt electrolyte under inert gas shielding, then takes out and obtains P (VDF-HFP) base gel polymer electrolyte film.
In described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF, acetonitrile or ethanol; Described pore creating material is ammonium carbonate, carbonic hydroammonium or urea; Described mixing time is 3～8 hours; Described barrier film is polypropylene non-woven fabric barrier film; Described vacuumize temperature is that 90～120 ℃, time are 24～48h.
In described step (b), the concentration of described lithium salt electrolyte is 0.5～1.5mol/l, the solute of described lithium salt electrolyte is that two (fluorine sulphonyl) imine lithiums, solvent are ethylene carbonate and methyl ethyl carbonate, and wherein, the volume ratio of ethylene carbonate and methyl ethyl carbonate is 2:5.
The present invention also comprises P (VDF-HFP) the base gel polymer electrolyte film that utilizes above-mentioned preparation method to make.
Above-mentioned P (VDF-HFP) base gel polymer electrolyte film can be assembled into lithium ion battery, this lithium ion battery comprises the dielectric film between positive electrode, negative electrode and described positive and negative electrode, described positive electrode comprises collector and is coated in this collector spreading mass, described dielectric film is above-mentioned P (VDF-HFP) base gel polymer electrolyte film, described slurry by nickel cobalt lithium oxide, acetylene black, Kynoar, 1-METHYLPYRROLIDONE in mass ratio 9:0.4:0.6:20 be uniformly mixed and form.
The present invention decomposes by pore creating material ammonium carbonate, carbonic hydroammonium or urea gases such as producing carbon dioxide, ammonia in the dry run of 90～120 ℃, these gases play the effect of pore-creating and form the gel-type polymer electrolyte film of loose structure in P (VDF-HFP), the gel-type polymer electrolyte film of this loose structure is more conducive to adsorb electrolyte, thereby improves conductivity.
The transfer function that the existing polymer segment of electrical conduction mechanism of gel-type polymer electrolyte film moves to lithium ion, has again the migration in the liquid microfacies that lithium ion provides at plasticizer.
The advantage of prepared P (VDF-HFP) the base gel polymer electrolyte film of the present invention is: 1, the present invention by pore creating material in the upper pore-creating of P (VDF-HFP), can effectively improve the conductivity of gel polymer electrolyte film, this gel polymer electrolyte film is assembled into after lithium ion battery, and the specific capacity of lithium ion battery is also improved.2, P (VDF-HFP) the base gel polymer electrolyte film that prepared by the present invention and current commercial liquid organic electrolyte (inflammable, volatile, thermal stability is bad etc.) are compared has good stability and fail safe.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.Following examples are for the present invention is described, to instruct those skilled in the art to realize the present invention, the present embodiment does not limit the present invention in any way.
The preparation process that the present invention prepares P (VDF-HFP) base gel polymer electrolyte film (hereinafter to be referred as gel polymer electrolyte film) is roughly divided into following two steps.(a) prepare P (VDF-HFP) base gelatin polymer film: 10:30 ~ 50:1 ~ 2 add respectively P (VDF-HFP), organic solvent and pore creating material in mass ratio in flask, and under inert gas shielding, stir 3-8h and make it mix the liquid that obtains thickness.Then, acquisition is cast in to PP(polypropylene) casting film-forming on nonwoven fabrics barrier film, and vacuum degree is 0.01MPa vacuumize 24-48h at 90-120 ℃.In the dry run of 90-120 ℃, pore creating material decomposes gases such as producing carbon dioxide, ammonia and plays the effect of pore-creating, thereby obtains described P (VDF-HFP) base gelatin polymer film.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: dried described P (VDF-HFP) base gelatin polymer film is put in the glove box that is full of argon gas, and be immersed in 10～60min in lithium salt electrolyte, then take out and obtain P (VDF-HFP) base gel polymer electrolyte film.
In described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF, acetonitrile or ethanol; Described pore creating material is ammonium carbonate, carbonic hydroammonium or urea.
In described step (b), the concentration of described lithium salt electrolyte is 0.5～1.5mol/l, in described lithium salt electrolyte, solute is two (fluorine sulphonyl) imine lithiums (LiFSI), solvent is ethylene carbonate (EC) and methyl ethyl carbonate (EMC), also can be abbreviated as LiFSI/EC+EMC, wherein, EC+EMC represents ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, volume ratio is 2:5, also can be abbreviated as the volume ratio 2:5 of EC:EMC, lower same.
The present invention also comprises and utilizes above-mentioned preparation method to make P (VDF-HFP) base gel polymer electrolyte film.
Above-mentioned P (VDF-HFP) base gel polymer electrolyte film can be assembled into lithium ion battery, this lithium ion battery comprises the dielectric film between positive electrode, negative electrode and described positive and negative electrode, described positive electrode comprises collector and is coated in this collector spreading mass, and described dielectric film is above-mentioned P (VDF-HFP) base gel polymer electrolyte film.
Described slurry by nickel cobalt lithium oxide, acetylene black, Kynoar, 1-METHYLPYRROLIDONE in mass ratio 9:0.4:0.6:20 be uniformly mixed and form.
The preparation method of described lithium ion battery is: 9:0.4:0.6:20 gets nickel cobalt lithium oxide, acetylene black, Kynoar, 1-METHYLPYRROLIDONE and fully stirs and make it to become the slurry mixing in mass ratio.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ° of C are dried to constant weight, and are pressed into cobalt nickel oxide lithium electrode in 12MPa pressure lower roll, and are cut into electrode film (be also described positive electrode, lower with).Lithium sheet is negative electrode.P of the present invention (VDF-HFP) base gel polymer electrolyte film is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
Below with 1～4 couple of P of the present invention of embodiment (VDF-HFP) base gel polymer electrolyte film and apply the preparation method that this gel polymer electrolyte film is assembled into lithium ion battery and be specifically described.
embodiment 1
In the embodiment of the present invention 1, the preparation method of gel polymer electrolyte film, comprises the steps.(a) prepare P (VDF-HFP) base gelatin polymer film: in flask, add respectively 10gP (VDF-HFP), 40gN-methyl pyrrolidone and 1.5g ammonium carbonate, and under inert gas shielding, stir 6h and make it mix the liquid that obtains thickness.Then, acquisition mucus is cast in to casting film-forming on polypropylene non-woven fabric barrier film, and vacuum degree is 0.01MPa vacuumize 30h at 100 ℃, thereby obtains described P (VDF-HFP) base gelatin polymer film.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: P (VDF-HFP) the base gelatin polymer film transfer that step (a) is prepared is to being full of in the glove box of argon gas, and immersed the volume ratio 2:5 of the LiFSI/EC+EMC(EC:EMC of 1.2mol/L) in 30min.Taken out and obtained P (VDF-HFP) base gel polymer electrolyte film.
The preparation method who the above-mentioned P making (VDF-HFP) base gel polymer electrolyte film is assembled into lithium ion battery is: take 9.0g nickel cobalt lithium oxide, 0.40g acetylene black, 0.60g Kynoar, 20gN-methyl pyrrolidone and fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ° of C are dried to constant weight, and are pressed into cobalt nickel oxide lithium electrode in 12MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned P (VDF-HFP) base gel polymer electrolyte film is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
embodiment 2
In the embodiment of the present invention 2, the preparation method of gel polymer electrolyte film comprises the steps.(a) prepare P (VDF-HFP) base gelatin polymer film: in flask, add respectively 10gP (VDF-HFP), 30g N; dinethylformamide and 1.0g carbonic hydroammonium, and under inert gas shielding, stir 8h and make it mix the liquid that obtains thickness.Then, acquisition mucus is cast in to casting film-forming on polypropylene non-woven fabric barrier film, and vacuum degree is 0.01MPa vacuumize 48h at 90 ℃, thereby obtains described P (VDF-HFP) base gelatin polymer film.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: P (VDF-HFP) the base gelatin polymer film transfer that step (a) is prepared is to being full of in the glove box of argon gas, and immersed the volume ratio 2:5 of the LiFSI/EC+EMC(EC:EMC of 0.5mol/L) in 60min.Taken out and obtained P (VDF-HFP) base gel polymer electrolyte film.
The preparation method who the above-mentioned P making (VDF-HFP) base gel polymer electrolyte film is assembled into lithium ion battery is: take 9.0g nickel cobalt lithium oxide, 0.40g acetylene black, 0.60g Kynoar, 20gN-methyl pyrrolidone and fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ° of C are dried to constant weight, and are pressed into cobalt nickel oxide lithium electrode in 12MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned P (VDF-HFP) base gel polymer electrolyte film is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
embodiment 3
In the embodiment of the present invention 3, the preparation method of gel polymer electrolyte film comprises the steps.(a) prepare P (VDF-HFP) base gelatin polymer film: in flask, add respectively 10gP (VDF-HFP), 50g acetonitrile and 2.0g urea, and under inert gas shielding, stir 3h and make it mix the liquid that obtains thickness.Then, acquisition mucus is cast in to casting film-forming on polypropylene non-woven fabric barrier film, and vacuum degree is 0.01MPa vacuumize 24h at 120 ℃, thereby obtains described P (VDF-HFP) base gelatin polymer film.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: P (VDF-HFP) the base gelatin polymer film transfer that step (a) is prepared is to being full of in the glove box of argon gas, and immersed the volume ratio 2:5 of the LiFSI/EC+EMC(EC:EMC of 1.5mol/L) in 10min.Taken out and obtained P (VDF-HFP) base gel polymer electrolyte film.
The preparation method who the above-mentioned P making (VDF-HFP) base gel polymer electrolyte film is assembled into lithium ion battery is: take 9.0g nickel cobalt lithium oxide, 0.40g acetylene black, 0.60g Kynoar, 20gN-methyl pyrrolidone and fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ° of C are dried to constant weight, and are pressed into cobalt nickel oxide lithium electrode in 12MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned P (VDF-HFP) base gel polymer electrolyte film is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
embodiment 4
In the embodiment of the present invention 1, the preparation method of gel polymer electrolyte film comprises the steps.(a) prepare P (VDF-HFP) base gelatin polymer film: in flask, add respectively 10gP (VDF-HFP), 45g ethanol and 1.7g urea; and under inert gas shielding, stir 6h make its mix obtain thickness liquid then; acquisition mucus is cast in to casting film-forming on polypropylene non-woven fabric barrier film; and vacuum degree is 0.01MPa vacuumize 36h at 110 ℃, thereby obtain described P (VDF-HFP) base gelatin polymer film.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: P (VDF-HFP) the base gelatin polymer film transfer that step (a) is prepared is to being full of in the glove box of argon gas, and immersed the volume ratio 2:5 of the LiFSI/EC+EMC(EC:EMC of 0.9mol/L) in 30min.Taken out and obtained P (VDF-HFP) base gel polymer electrolyte film.
The preparation method who the above-mentioned P making (VDF-HFP) base gel polymer electrolyte film is assembled into lithium ion battery is: take 9.0g nickel cobalt lithium oxide, 0.40g acetylene black, 0.60g Kynoar, 20gN-methyl pyrrolidone and fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ° of C are dried to constant weight, and are pressed into cobalt nickel oxide lithium electrode in 12MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned P (VDF-HFP) base gel polymer electrolyte film is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
comparative example
The preparation method of comparative example P of the present invention (VDF-HFP) base gel polymer electrolyte film comprises the steps.(a) prepare P (VDF-HFP) base gelatin polymer film: in flask, add respectively 10gP (VDF-HFP), 40g acetonitrile, and under inert gas shielding, stir 6h and make it mix the liquid that obtains thickness.Finally, acquisition mucus is cast in to casting film-forming on polypropylene non-woven fabric barrier film, and vacuum degree is 0.01MPa vacuumize 36h at 100 ℃, thereby obtains described P (VDF-HFP) base gelatin polymer film.Be not add pore creating material with the difference of above-described embodiment.(b) prepare P (VDF-HFP) base gel polymer electrolyte film: P (VDF-HFP) the base gelatin polymer film transfer that step (a) is prepared is to being full of in the glove box of argon gas, and immersed the volume ratio 2:5 of the LiFSI/EC+EMC(EC:EMC of 1.2mol/L) in 30min.Taken out and obtained P (VDF-HFP) base gel polymer electrolyte film.
The preparation method who the above-mentioned P making (VDF-HFP) base gel polymer electrolyte film is assembled into lithium ion battery is: take 9.0g nickel cobalt lithium oxide, 0.40g acetylene black, 0.60g Kynoar, 20gN-methyl pyrrolidone and fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ° of C are dried to constant weight, and are pressed into cobalt nickel oxide lithium electrode in 12MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned P (VDF-HFP) base gel polymer electrolyte film is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
The method of testing of the conductivity of prepared P (VDF-HFP) base gel polymer electrolyte film is: between two stainless steel blocking electrodes, add P (VDF-HFP) the base gel polymer electrolyte film preparing, form the electrode system that polymer dielectric film blocks, do ac impedance measurement, obtain the complex impedance plane graph of GPE.
The curve of described figure is the body impedance of described P (VDF-HFP) base gel polymer electrolyte film in the intersection value of high frequency region and transverse axis.According to the body impedance (R of described P (VDF-HFP) base gel polymer electrolyte film
b) and its conductivity (σ) between relation:
σ=d/(S*?R
b)
Can calculate the conductivity (σ) of described P (VDF-HFP) base gel polymer electrolyte film, wherein d is that thickness, the S of described P (VDF-HFP) base gel polymer electrolyte film are the contact area of described P (VDF-HFP) base gel polymer electrolyte film and described stainless steel blocking electrode.The conductivity that table 1 is P (VDF-HFP) base gel polymer electrolyte film in the present embodiment and the lithium ion battery assembling carry out the performance data of 0.2C charge-discharge test in 2.5～4.2 voltage range by charge-discharge test instrument pond.
Table 1
| Table 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| The conductivity ms/cm of prepared P (VDF-HFP) base gel polymer electrolyte film | 5.5 | 4.1 | 4.9 | 5.2 | 1.2 |
| The lithium ion battery first discharge specific capacity mAh/g assembling | 125 | 112 | 117 | 123 | 103 |
As can be seen from Table 1, the conductivity of P (VDF-HFP) the base gel polymer electrolyte film of preparing by embodiment 1～4 method is greater than the conductivity of comparative example, and reaches 5.5ms/cm in embodiment 1; All be greater than the specific capacity in comparative example by the first discharge specific capacity of the lithium ion battery of embodiment 1～4 method assembling, and arrived 125mAh/g than electric capacity in embodiment 1.
Can draw such conclusion from above data, the present invention is by pore creating material pore-creating on P (VDF-HFP), can effectively improve the conductivity of gel polymer electrolyte film, this gel polymer electrolyte film is assembled into after lithium ion battery, and the specific capacity of lithium ion battery is also improved.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection range of claims.
Claims (10)
1. a preparation method for P (VDF-HFP) base gel polymer electrolyte film, is characterized in that, comprises the steps:
(a) prepare P (VDF-HFP) base gelatin polymer film: under inert gas shielding, P (VDF-HFP), organic solvent and pore creating material are stirred 10:30 ~ 50:1 ~ 2 in mass ratio, mix to obtain mucus, be cast in casting film-forming on barrier film, after vacuumize, obtain described P (VDF-HFP) base gelatin polymer film;
(b) prepare P (VDF-HFP) base gel polymer electrolyte film: 10～60min during dried described P (VDF-HFP) base gelatin polymer film is immersed in to lithium salt electrolyte under inert gas shielding, then takes out and obtains P (VDF-HFP) base gel polymer electrolyte film.
2. preparation method according to claim 1, is characterized in that, in described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF, acetonitrile or ethanol.
3. preparation method according to claim 1, is characterized in that, in described step (a), described pore creating material is ammonium carbonate, carbonic hydroammonium or urea.
4. preparation method according to claim 1, is characterized in that, in described step (a), described mixing time is 3～8 hours.
5. preparation method according to claim 1, is characterized in that, in described step (a), described barrier film is polypropylene non-woven fabric barrier film.
6. preparation method according to claim 1, is characterized in that, in described step (a), described vacuumize temperature is that 90～120 ℃, time are 24～48h.
7. preparation method according to claim 1, it is characterized in that, in described step (b), the concentration of described lithium salt electrolyte is 0.5～1.5mol/l, the solute of described lithium salt electrolyte is that two (fluorine sulphonyl) imine lithiums, solvent are ethylene carbonate and methyl ethyl carbonate, wherein, the volume ratio of ethylene carbonate and methyl ethyl carbonate is 2:5.
8. P (VDF-HFP) the base gel polymer electrolyte that the arbitrary described preparation method of claim 1 to 7 makes.
9. a lithium ion battery, comprise the dielectric film between positive electrode, negative electrode and described positive and negative electrode, described positive electrode comprises collector and is coated in this collector spreading mass, it is characterized in that, described dielectric film is P claimed in claim 8 (VDF-HFP) base gel polymer electrolyte film.
10. lithium ion battery according to claim 9, is characterized in that, described slurry by nickel cobalt lithium oxide, acetylene black, Kynoar, 1-METHYLPYRROLIDONE in mass ratio 9:0.4:0.6:20 be uniformly mixed and form.
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