CN1438272A - Polymer electrolyte for lithium-ion cell and preparation method - Google Patents

Polymer electrolyte for lithium-ion cell and preparation method Download PDF

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CN1438272A
CN1438272A CN03100742A CN03100742A CN1438272A CN 1438272 A CN1438272 A CN 1438272A CN 03100742 A CN03100742 A CN 03100742A CN 03100742 A CN03100742 A CN 03100742A CN 1438272 A CN1438272 A CN 1438272A
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lithium
polymer
ion battery
polymer dielectric
lithium ion
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CN1189514C (en
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唐致远
王占良
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Tianjin University
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Tianjin University
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    • 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
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention refers to a polymer electrolyte used in lithium cell as well as the making method, including polymer base material (A) and (B) and liquid electrolyte solution (C) which contains a lithium salt and proton inert solvent. A is poly(methyl methacrylate-acylic nitrile-methacrylate lithium) (P(MMA-AN-MALi), PMAML, the molar composition of the components: 40%<AN<90%, 10%<MMAM<40%, and 0%<MALi<20%. B is the polyvinylidene (PVDF) or the poly (polyvinylidene-hexafluoro propylene), P(VDF-HFP). Its film can be one-step obtained by volatilizing agent, the conductivity at room temperature high (3.2X10 to the power -3 S.cm-1).

Description

Be used for polymer dielectric of lithium ion battery and preparation method thereof
Technical field
The present invention relates to a kind of ionogen that is used for lithium ion battery and preparation method thereof, more particularly relate to a kind of polymer dielectric that is used for lithium ion battery and preparation method thereof.
Background technology
Polymer Li-ion battery has that energy density height, no electrolyte leakage problem, safety performance are good, flexible design, be easy to characteristics such as scale operation.Along with the continuous miniaturization of electron device, secondary cell also will develop to the ultrafine direction of light weight.And be that electrolytical lithium ion battery can satisfy this requirement with polymer materials.
In the existing polymer dielectric,, can't satisfy the requirement that practicability is produced because specific conductivity is too low under pure solid polymer electrolyte (not plasticizer-containing) room temperature.Although reported many methods, attempting is not having to prepare solid polymer electrolyte under the situation of solvent, and the none system is proved to be gratifying.Therefore, present research work about polymer dielectric mainly concentrates on gel polymer electrolyte.Contain a large amount of organic softening agent in such polymer dielectric, the specific conductivity under its room temperature can reach 1 * 10 -3Scm -1More than.Study more polymer electrolyte system and mainly contain several big classes such as PEO, PAN, PMMA, PVDF, PVC.At present, the subject matter one of polymer dielectric existence is the contradiction between mechanical property and the specific conductivity.In order to improve the room-temperature conductivity of gel polymer electrolyte, need in polymeric matrix, solidifying a large amount of organic softening agent, this can make its physical strength decline to a great extent.The 2nd, interface stability is poor between ionogen and electrode.Along with charge and discharge cycles number of times or the increase of storage period, polymer dielectric and interelectrode interface impedance also can constantly increase, and this will influence the charge-discharge performance of battery.The 3rd, complicated process of preparation.No matter be the method or the phase inversion method of extraction pore-forming material, in scale operation, all exist many inconvenience, its complex manufacturing.
Summary of the invention
The present invention is in order to overcome weak point of the prior art, to provide a kind of preparation technology easy, room-temperature conductivity height, polymer dielectric that interface stability is good and preparation method thereof.
The present invention is achieved through the following technical solutions:
A kind of polymer dielectric that is used for lithium ion battery, it is made up of polymeric matrix and electrolytic solution, the self-supported membrane that described polymeric matrix is made up of two kinds of polymer materials A and B, described polymer materials A is poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium), described polymer materials B is polyvinylidene difluoride (PVDF) or poly-(biasfluoroethylene-hexafluoropropylene), contains dissociable lithium salts and aprotic solvent in the described electrolytic solution.The mole composition of each component is respectively 40%＜vinyl cyanide＜90%, 10%＜methyl methacrylate＜40%, 0＜methacrylic acid lithium＜20% in matrix material A; Contain the electrolytic solution that weight percent is 20-80% in the polymer dielectric.In the mixture of matrix material A and B, the mass ratio of A and B is 1: 10～2: 3.
The present invention also provides a kind of method for preparing polymer electrolytes that is used for lithium ion battery, and it comprises the following steps:
(1) monomers methyl methacrylate, vinyl cyanide, methacrylic acid lithium are purified;
(2) getting above-mentioned each monomer is dissolved in and makes monomer mixture in the solvent;
(3) above-mentioned monomer mixture is packed in the container, and add initiator;
(4) feeding nitrogen is removed the oxygen in the container, sealed vessel afterwards; Reacted 8～12 hours down at 50～70 ℃, promptly make matrix material A i.e. poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium);
(5) be polyvinylidene difluoride (PVDF) with above-mentioned matrix material A promptly poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium) and polymer materials B or gather (biasfluoroethylene-hexafluoropropylene) and mix and fully dissolve with solvent;
(6) above-mentioned solution is poured on makes film on the flat board;
(7) with above-mentioned film vacuum-drying;
(8) be 20%～80% with above-mentioned exsiccant film with electrolytic solution dipping 30～60 minutes to film liquid holdup, promptly make the polymer dielectric that is used for lithium ion battery.
Contain dissociable lithium salts and aprotic solvent in the above-mentioned electrolytic solution.
The present invention has following beneficial effect: polymer dielectric makes by the solvent flashing single stage method, and preparation technology is easy, and the polymer dielectric specific conductivity height, the interface stability that make are good.
Description of drawings
The alternating-current impedance of Fig. 1 Li/ polymer dielectric/Li battery;
The alternating-current impedance of Fig. 2 Li/ polymer dielectric 2/Li battery.
Embodiment
The raw materials used methyl methacrylate MMA that mainly contains during the synthesizing new matrix material among the present invention, vinyl cyanide is AN, the methacrylic acid lithium is MALi.Above-mentioned three kinds of raw materials make promptly poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium) (P (MMA-AN-MALi)) of matrix material A through polyreaction, brief note is PMAML, wherein the mole composition of each component is respectively, 40%＜AN＜90%, 10%＜MMA＜40%, 0＜MALi＜20%.Matrix material B is that polyvinylidene difluoride (PVDF) is that PVDF or poly-(biasfluoroethylene-hexafluoropropylene) are P (VDF-HFP).Matrix material A be dissolved in the solvent after B mixes, make polymer electrolyte matrices by the solvent flashing single stage method.The electrolyte matrix that makes is immersed in promptly makes polymer dielectric in the electrolytic solution.Contain lithium salts and aprotic solvent in the electrolytic solution.Lithium salts is LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiCF 3SO 3, LiN (CF 3SO 2) 2In a kind of.Aprotic solvent is one or more among EC (NSC 11801), PC (propylene carbonate), DEC (diethyl carbonate), DMC (methylcarbonate), DME (diethyl carbonate), the EMC (carbon ester methyl ethyl ester).
The invention will be further described below in conjunction with specific embodiment.
MMA and AN remove stopper with 0.5% sodium hydroxide solution before use, handle after underpressure distillation and with molecular sieve drying.The solution polymerization process of example 1:PMAML.0.15mol MMA, 0.8mol AN and 0.05mol MALi are made monomer mixture with 150ml DMF (dimethyl formamide) or dissolve with methanol, the monomer mixture that is made into is packed in the sealable Glass Containers, the Diisopropyl azodicarboxylate initiator that adds 0.3g, and remove oxygen in the container with exsiccant nitrogen, reaction vessel is sealed.React 8h down at 50 ℃ then and can make PMAML.Example 2:, synthesized the PMAML of several different ratioss by the polymerizing condition in the example 1.Each component MMA, AN and MALi are respectively by 0.4mol, 0.4mol, 0.2mol and 0.1mol, 0.8mol, the 0.1mol polymerization that feeds intake among the PMAML, the amount of solvent for use is respectively 100ml and 150ml, the initiator benzoyl peroxide is respectively 0.40g and 0.27g, temperature of reaction is respectively 60 ℃ and 70 ℃, and the reaction times was respectively 10 and 12 hours.Example 3: the method by example 1 prepares PMAML.1g PMAML and 2g P (VDF-HFP) with fully dissolving of 15gDMF (or a kind of among the NMP, acetone, DMF or mix), are made film then on smooth sheet glass, and vacuum-drying.Resulting polymer film thickness is about 50 μ m, floods 30-60min with electrolytic solution, and lithium salts is LiPF in the electrolytic solution 6, solvent is EC/DEC (EC and DEC weight ratio are 1: 1, and lithium salt is 1M).Made polymer dielectric film liquid holdup is 80%.The polymer dielectric specific conductivity adopts stainless steel electrode/polymer dielectric/stainless steel electrode battery testing, and the area of polymer dielectric film is about 1.2cm 2, utilize ac impedance technology to measure specific conductivity, its room-temperature conductivity is 3.2 * 10 -3Scm -1Example 4: the method by example 3 prepares polymer dielectric, and wherein the consumption of PMAML and P (VDF-HFP) is respectively 1g and 5g in the polymeric matrix.When the electrolyte solution volume of holding was 40% in the polymer dielectric, specific conductivity was 7.8 * 10 under the room temperature -5Scm -1(the 1M LiBF of electrolytic solution in polymer dielectric 4-EC/DMC) the volume of holding is 60% o'clock, and specific conductivity is 1.48 * 10 under the room temperature -3Scm -1Its electrochemical stability window is greater than 4.5V.Example 5: select for use PVDF base porous polymer electrolyte as the reference sample, and assembling Li/ polymer dielectric/Li test battery, the interface impedance is with the changing conditions of storage period between research polymer dielectric and lithium electrode.PVDF based polyalcohol film makes by phase inversion method, and wherein film-casting liquid consists of deionized water, acetone and PVDF, and its weight is respectively 1g, 8g and 1g.Liquid electrolyte solution (1M LiBF in the polymer dielectric 4-EC/DMC) volume of holding is about 72%.Interface impedance adopts ac impedance technology to measure at electrochemical workstation, and electrode diameter is 12mm when wherein testing, test frequency scope 1MHz-10mHz, and response signal is 10mV, test result is as shown in Figure 1.Example 6: example 4 prepared polymer dielectric films are assembled into Li/ polymer dielectric/Li test battery in glove box, in order to measure the interface impedance between polymer dielectric and metal lithium electrode.Fig. 2 has provided the ac impedance spectroscopy at open-circuit condition discharge different time, and semicircle diameter big among the figure is corresponding with polymer dielectric and interelectrode interface impedance.Can find out, along with the prolongation interface impedance of storage period also can increase gradually.But it gathers way and not quite, and after placing for two weeks, interface impedance tends towards stability substantially, and this illustrates that this polymer electrolyte system and interelectrode interfacial property stablize.And the interface impedance between PVDF base polymer electrolyte shown in Figure 1 and metal lithium electrode is bigger with prolonging the interface impedance increase storage period, places rear interface impedance in 19 days and still fails to stablize.Hence one can see that, the introducing of PMAML make polymer dielectric interfacial property be improved significantly, stable by the polymer dielectric interfacial property of example 3 methods preparations.Example 7: the method by example 3 has prepared a kind of polymer dielectric in order to the assembling polymer Li-ion battery, and wherein the quality of polymeric matrix PMAML and P (VDF-HFP) is respectively 1g and 9g, and electrolytic solution is 1.2MLiPF 6-EC/DEC/EMC (1: 1: 1wt%).Positive electrode active material is a cobalt acid lithium, and the weight of each component is respectively in the pole piece: cobalt acid lithium 8.5g, graphitized carbon black (super-p) 1.0g, binding agent PVDF 0.5g.The used active substance of negative pole is a graphitized carbon fibre, and the weight of each component is respectively in the pole piece: carbon fiber 9.0g, graphitized carbon black (super-p) 0.3g, binding agent PVDF 0.7g.Fig. 3 has provided the typical charging and discharging curve of made polymer Li-ion battery, and wherein scheming to go up transverse axis is the specific storage of positive electrode active material.The coulombic efficiency of first charge-discharge is 91%, and irreversible capacity is little, and discharge presses platform area more than 3.6V.

Claims (6)

1, a kind of polymer dielectric that is used for lithium ion battery, it is characterized in that, it is made up of polymeric matrix and electrolytic solution, the self-supported membrane that described polymeric matrix is made up of two kinds of polymer materials A and B, described polymer materials A is poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium), described polymer materials B is polyvinylidene difluoride (PVDF) or poly-(biasfluoroethylene-hexafluoropropylene), contains dissociable lithium salts and aprotic solvent in the described electrolytic solution.
2, the polymer dielectric that is used for lithium ion battery according to claim 1, the mole composition that it is characterized in that each component among the described matrix material A is respectively, 40%＜vinyl cyanide＜90%, 10%＜methyl methacrylate＜40%, 0＜methacrylic acid lithium＜20%.
3, the polymer dielectric that is used for lithium ion battery according to claim 1 is characterized in that, contains the electrolytic solution that weight percent is 20-80% in the described polymer dielectric.
4, the polymer dielectric that is used for lithium ion battery according to claim 1 is characterized in that, in the mixture of described matrix material A and B, the mass ratio of A and B is 1: 10～2: 3.
5, a kind of described method for preparing polymer electrolytes that is used for lithium ion battery of claim 1 for preparing is characterized in that it comprises the following steps:
(1) monomers methyl methacrylate, vinyl cyanide, methacrylic acid lithium are purified;
(2) getting above-mentioned each monomer is dissolved in and makes monomer mixture in the solvent;
(3) above-mentioned monomer mixture is packed in the container, and add initiator;
(4) feeding nitrogen is removed the oxygen in the container, sealed vessel afterwards; Reacted 8～12 hours down at 50～70 ℃, promptly make matrix material A i.e. poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium);
(5) be polyvinylidene difluoride (PVDF) with above-mentioned matrix material A promptly poly-(methyl methacrylate-vinyl cyanide-methacrylic acid lithium) and polymer materials B or gather (biasfluoroethylene-hexafluoropropylene) and mix and fully dissolve with solvent;
(6) above-mentioned solution is poured on makes film on the flat board;
(7) with above-mentioned film vacuum-drying;
(8) be 20%～80% with above-mentioned exsiccant film with electrolytic solution dipping 30～60 minutes to film liquid holdup, promptly make the polymer dielectric that is used for lithium ion battery.
6, the method for preparing polymer electrolytes that is used for lithium ion battery according to claim 5 is characterized in that, contains dissociable lithium salts and aprotic solvent in the described electrolytic solution.
CNB031007422A 2003-01-23 2003-01-23 Polymer electrolyte for lithium-ion cell and preparation method Expired - Fee Related CN1189514C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100401574C (en) * 2006-03-15 2008-07-09 上海南都能源科技有限公司 Gel synergizing type polymer lithium ion battery and preparation method thereof
CN101200568B (en) * 2006-12-14 2011-04-13 西北工业大学 Gel polymer electrolytes and preparation method thereof
CN108550908A (en) * 2018-06-08 2018-09-18 东莞市杉杉电池材料有限公司 A kind of lithium ion battery polymer electrolyte film and preparation method thereof
CN112239519A (en) * 2020-09-30 2021-01-19 氟金(上海)新材料有限公司 Lithium carbonate-containing ionic copolymer and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100524936C (en) * 2007-08-23 2009-08-05 广州天赐高新材料股份有限公司 Micro joint gel state lithium ion battery polymer electrolyte film and its making method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100401574C (en) * 2006-03-15 2008-07-09 上海南都能源科技有限公司 Gel synergizing type polymer lithium ion battery and preparation method thereof
CN101200568B (en) * 2006-12-14 2011-04-13 西北工业大学 Gel polymer electrolytes and preparation method thereof
CN108550908A (en) * 2018-06-08 2018-09-18 东莞市杉杉电池材料有限公司 A kind of lithium ion battery polymer electrolyte film and preparation method thereof
CN112239519A (en) * 2020-09-30 2021-01-19 氟金(上海)新材料有限公司 Lithium carbonate-containing ionic copolymer and preparation method thereof

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