CN103840203A - PAN (Polyacrylonitrile)-based gel polymer electrolyte membrane, preparation method of membrane, and lithium ion battery - Google Patents
PAN (Polyacrylonitrile)-based gel polymer electrolyte membrane, preparation method of membrane, and lithium ion battery Download PDFInfo
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- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 81
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229920002239 polyacrylonitrile Polymers 0.000 title abstract description 88
- 239000012528 membrane Substances 0.000 title abstract 8
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 239000000499 gel Substances 0.000 claims description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 108010010803 Gelatin Proteins 0.000 claims description 24
- 239000008273 gelatin Substances 0.000 claims description 24
- 229920000159 gelatin Polymers 0.000 claims description 24
- 235000019322 gelatine Nutrition 0.000 claims description 24
- 235000011852 gelatine desserts Nutrition 0.000 claims description 24
- 229920006254 polymer film Polymers 0.000 claims description 24
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 15
- 229910017052 cobalt Inorganic materials 0.000 claims description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 15
- -1 polypropylene Polymers 0.000 claims description 13
- 230000004888 barrier function Effects 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004745 nonwoven fabric Substances 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- 210000003097 mucus Anatomy 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011244 liquid electrolyte Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229920005597 polymer membrane Polymers 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 229910013188 LiBOB Inorganic materials 0.000 description 7
- 239000005030 aluminium foil Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a PAN (Polyacrylonitrile)-based gel polymer electrolyte membrane. The preparation method comprises the following steps: (a) preparing a PAN-based gel polymer membrane; and (b) preparing the PAN-based gel polymer electrolyte membrane. The invention also relates to a lithium ion battery assembled through the PAN-based gel polymer electrolyte membrane. According to the preparation method, pores are formed in PAN through a pore forming agent, so that the conductivity of the gel polymer electrolyte membrane is effectively improved; after the gel polymer electrolyte membrane is assembled to be the lithium ion battery, the specific capacity of the lithium ion battery is increased; in addition, compared with the current commercial organic liquid electrolyte, the PAN-based gel polymer electrolyte membrane prepared by adopting the preparation method has the relatively high stability and safety.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to PAN (polyacrylonitrile) base gel polymer electrolyte film and preparation method thereof.The invention still further relates to and adopt the prepared lithium ion battery of this PAN 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 PAN base gel polymer electrolyte film and preparation method thereof and the lithium ion battery that adopts this PAN 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: a kind of preparation method of PAN base gel polymer electrolyte film, comprises the steps.(a) prepare PAN(polypropylene fine) base gelatin polymer film: under inert gas shielding, PAN, 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 PAN base gelatin polymer film; (b) prepare PAN base gel polymer electrolyte film: 10～60min during dried described PAN base gelatin polymer film is immersed in to lithium salt electrolyte under inert gas shielding, then takes out and obtains PAN base gel polymer electrolyte film.
In described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF or acetonitrile; 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 DEG C, 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 dioxalic acid lithium borate, solvent are ethylene carbonate and methyl ethyl carbonate, and wherein, the volume ratio of ethylene carbonate and methyl ethyl carbonate is 1:3.
The present invention also comprises the PAN base gel polymer electrolyte film that utilizes above-mentioned preparation method to make.
Above-mentioned PAN 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 PAN base gel polymer electrolyte film, described slurry by cobalt acid lithium, acetylene black, Kynoar, 1-METHYLPYRROLIDONE in mass ratio 9:0.5:0.5:20 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 DEG C, these gases play the effect of pore-creating and form the gel-type polymer electrolyte film of loose structure in PAN, 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 the prepared PAN base gel polymer electrolyte film of the present invention is: 1, the present invention is by pore creating material pore-creating on PAN, 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, the PAN 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 PAN base gel polymer electrolyte film (hereinafter to be referred as gel polymer electrolyte film) is roughly divided into following two steps.(a) prepare PAN base gelatin polymer film: 10:30 ~ 50:1 ~ 2 add respectively PAN, 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.Finally, 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 DEG C.In the dry run of 90-120 DEG C, pore creating material decomposes gases such as producing carbon dioxide, ammonia and plays the effect of pore-creating, thereby obtains described PAN base gelatin polymer film.(b) prepare PAN base gel polymer electrolyte film: dried described PAN 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 PAN base gel polymer electrolyte film.
In described step (a), described organic solvent is 1-METHYLPYRROLIDONE, DMF or acetonitrile; 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 dioxalic acid lithium borate (LiBOB), solvent is ethylene carbonate (EC) and methyl ethyl carbonate (EMC), also can be abbreviated as under LiBOB/EC+EMC(same), wherein, EC+EMC represents ethylene carbonate (EC) and methyl ethyl carbonate (EMC) mixed solvent, volume ratio is 1:3, also can be abbreviated as the volume ratio 1:3 of EC:EMC, lower same.
The present invention also comprises and utilizes above-mentioned preparation method to make PAN base gel polymer electrolyte film.
Above-mentioned PAN 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 PAN base gel polymer electrolyte film.
Described slurry by cobalt acid lithium, acetylene black, Kynoar, 1-METHYLPYRROLIDONE in mass ratio 9:0.5:0.5:20 be uniformly mixed and form.
The preparation method of described lithium ion battery is: 9:0.5:0.5:20 gets cobalt acid lithium, 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 acid lithium electrode in 13MPa pressure lower roll, and are cut into electrode film (be also described positive electrode, lower with).Lithium sheet is negative electrode.PAN base gel polymer electrolyte film of the present invention is placed between described positive and negative electrode, and on stamping machine, fastening lithium ionic cell is made in sealing.
Below with 1～4 pair of PAN base gel polymer electrolyte film of the present invention of embodiment 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 PAN base gelatin polymer film: in flask, add respectively 10gPAN, 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 DEG C, thereby obtains described PAN base gelatin polymer film.(b) prepare PAN base gel polymer electrolyte film: the PAN 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 1:3 of the LiBOB/EC+EMC(EC:EMC of 1.2mol/L) in 30min.Taken out and obtained PAN base gel polymer electrolyte film.
The preparation method that the above-mentioned PAN base gel polymer electrolyte film making is assembled into lithium ion battery is: take 9.0g cobalt acid lithium, 0.5g acetylene black, 0.5g 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 acid lithium electrode in 13MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned PAN 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 PAN base gelatin polymer film: in flask, add respectively 10gPAN, 30g DMF 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 DEG C, thereby obtains described PAN base gelatin polymer film.(b) prepare PAN base gel polymer electrolyte film: the PAN 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 1:3 of the LiBOB/EC+EMC(EC:EMC of 0.5mol/L) in 60min.Taken out and obtained PAN base gel polymer electrolyte film.
The preparation method that the above-mentioned PAN base gel polymer electrolyte film making is assembled into lithium ion battery is: take 9.0g cobalt acid lithium, 0.5g acetylene black, 0.5g 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 acid lithium electrode in 13MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned PAN 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 PAN base gelatin polymer film: in flask, add respectively 10gPAN, 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 DEG C, thereby obtains described PAN base gelatin polymer film.(b) prepare PAN base gel polymer electrolyte film: the PAN 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 1:3 of the LiBOB/EC+EMC(EC:EMC of 1.5mol/L) in 10min.Taken out and obtained PAN base gel polymer electrolyte film.
The preparation method that the above-mentioned PAN base gel polymer electrolyte film making is assembled into lithium ion battery is: take 9.0g cobalt acid lithium, 0.5g acetylene black, 0.5g 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 acid lithium electrode in 13MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned PAN 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 4, the preparation method of gel polymer electrolyte film comprises the steps.(a) prepare PAN base gelatin polymer film: in flask, add respectively 10gPAN, 45N, dinethylformamide and 1.7g urea, 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 36h at 110 DEG C, thereby obtains described PAN base gelatin polymer film.(b) prepare PAN base gel polymer electrolyte film: the PAN 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 1:3 of the LiBOB/EC+EMC(EC:EMC of 0.9mol/L) in 30min.Taken out and obtained PAN base gel polymer electrolyte film.
The preparation method that the above-mentioned PAN base gel polymer electrolyte film making is assembled into lithium ion battery is: take 9.0g cobalt acid lithium, 0.5g acetylene black, 0.5g 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 acid lithium electrode in 13MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned PAN 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 PAN base gel polymer electrolyte film of the present invention comprises the steps.(a) prepare PAN base gelatin polymer film: in flask, add respectively 10gPAN, 40g acetonitrile, 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 36h at 100 DEG C, thereby obtains PAN base gelatin polymer film.Be not add pore creating material with the difference of above-described embodiment.(b) prepare PAN base gel polymer electrolyte film: the PAN 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 1:3 of the LiBOB/EC+EMC(EC:EMC of 1.2mol/L) in 30min.Taken out and obtained PAN base gel polymer electrolyte film.
The preparation method that the above-mentioned PAN base gel polymer electrolyte film making is assembled into lithium ion battery is: take 9.0g cobalt acid lithium, 0.5g acetylene black, 0.5g 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 acid lithium electrode in 13MPa pressure lower roll, and are cut into electrode film.Lithium sheet is negative electrode.Above-mentioned PAN 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 PAN base gel polymer electrolyte film is: between two stainless steel blocking electrodes, add the PAN 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 PAN base gel polymer electrolyte film in the intersection value of high frequency region and transverse axis.According to the body impedance (R of described PAN base gel polymer electrolyte film
b) and its conductivity (σ) between relation:
σ=d/(S*?R
b)
Can calculate the conductivity (σ) of described PAN base gel polymer electrolyte film, wherein d is that thickness, the S of described PAN base gel polymer electrolyte film are the contact area of described PAN base gel polymer electrolyte film and described stainless steel blocking electrode.The conductivity that table 1 is PAN base gel polymer electrolyte film prepared in the present embodiment and the lithium ion battery assembling carry out the performance data of 0.1 C charge-discharge test in 2.5～4.2 voltage range by charge-discharge test instrument.
Table 1
| Table 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example |
| The conductivity ms/cm of prepared PAN base gel polymer electrolyte film | 4.8 | 3.5 | 4.1 | 4.3 | 1.1 |
| The lithium ion battery first discharge specific capacity mAh/g assembling | 118 | 102 | 106 | 110 | 96 |
As can be seen from Table 1, the conductivity of the PAN base gel polymer electrolyte film preparing by embodiment 1～4 method is greater than the conductivity of comparative example, and reaches 4.8ms/cm in embodiment 1; The first discharge specific capacity of the lithium ion battery assembling by embodiment 1～4 method is all greater than the specific capacity in comparative example, and has arrived 118mAh/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 PAN, the conductivity that can effectively improve gel polymer electrolyte film, is assembled into this gel polymer electrolyte film 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 skill in the art are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or amendment, 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 PAN base gel polymer electrolyte film, is characterized in that, comprises the steps:
(a) prepare PAN base gelatin polymer film: under inert gas shielding, PAN, 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 PAN base gelatin polymer film;
(b) prepare PAN base gel polymer electrolyte film: 10～60min during dried described PAN base gelatin polymer film is immersed in to lithium salt electrolyte under inert gas shielding, then takes out and obtains PAN 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 or acetonitrile.
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 DEG C, 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 dioxalic acid lithium borate, solvent are ethylene carbonate and methyl ethyl carbonate, wherein, the volume ratio of ethylene carbonate and methyl ethyl carbonate is 1:3.
8. the PAN base gel polymer electrolyte film 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 PAN base gel polymer electrolyte film claimed in claim 8.
10. lithium ion battery according to claim 9, is characterized in that, described slurry by cobalt acid lithium, acetylene black, Kynoar, 1-METHYLPYRROLIDONE in mass ratio 9:0.5:0.5:20 be uniformly mixed and form.
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| CN114976233A (en) * | 2022-06-21 | 2022-08-30 | 合肥国轩高科动力能源有限公司 | Composite gel polymer electrolyte and preparation method and application thereof |
| CN117293394A (en) * | 2023-11-24 | 2023-12-26 | 深圳市本征方程石墨烯技术股份有限公司 | Electrolyte and preparation method and application thereof |
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| CN102244292A (en) * | 2011-06-09 | 2011-11-16 | 华南师范大学 | Lithium ion battery ionic liquid based gel polymer electrolyte as well as preparation and applications thereof |
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Application publication date: 20140604 |