CN102286158B - Method for preparing porous composite polymer electrolyte film through gas volatilization - Google Patents
Method for preparing porous composite polymer electrolyte film through gas volatilization Download PDFInfo
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- CN102286158B CN102286158B CN2011101706314A CN201110170631A CN102286158B CN 102286158 B CN102286158 B CN 102286158B CN 2011101706314 A CN2011101706314 A CN 2011101706314A CN 201110170631 A CN201110170631 A CN 201110170631A CN 102286158 B CN102286158 B CN 102286158B
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Abstract
The invention relates to a composite polymer porous film which contains a polymer, can be subjected to thermal decomposition to obtain a gaseous compound at a low temperature and may contain inorganic adding particles. The method comprises the following steps: a casting film solution which can be subjected to thermal decomposition at a low temperature to form the gaseous compound is added to prepare a wet film, the wet film is dried at 40-90 DEG C in vacuum atmosphere, air atmosphere or other atmospheres, and the gas which can be subjected to thermal decomposition at a low temperature to form the gaseous compound, in the casting solution is used to form pores and obtain the porous film. After the obtained polymer electrolyte film is soaked in an EC-DMC-EMC lithium salt solution to soak, activate and plasticize, the film has good electrochemical property. The obtained polymer electrolyte film has good mechanical strength and flexibility, high ionic conductivity and good electrochemical property; and industrial production is easy to realize.
Description
Technical field
The present invention relates to a kind of polymer electrolyte film preparation method of lithium ion battery.
Background technology
Along with becoming increasingly conspicuous of problems such as environmental pollution, energy dilemma and shortage of resources, development of technologies such as countries in the world are more and more highly paid attention to efficiently, cleaning, renewable energy source and electric vehicle.
In recent years along with the development of the popularizing of portable electric appts, power truck, obtained great concern as the lithium ion battery of high capacity power source of new generation.And gel polymer electrolyte lithium-ion battery is owing to not only have height ratio capacity, high working voltage, high cycle life, memory-less effect and advantages of environment protection; And safety, snappiness are good, be prone to processing; Since 1999 put on market, caused people's extensive concern immediately.The required polymer dielectric film of battery must have ionic conductivity preferably, to guarantee battery lower internal resistance is arranged; It also need have good mechanical properties in practical application.
Bellcore company reported first in 1994 is that filmogen, Witcizer 300 (DBP) are the filming technology of pore-forming material with PVDF; With a kind of volatile organic solvent DBP is extracted from film again after the film forming; Thereby in film, formed the aperture of millimicro meter level; Bellcore system embrane method that Here it is has early realized commercial applications.But its shortcoming is that the polymer thin film dynamic performance that makes is relatively poor, and processability is not good, has limited it and has promoted the use of.As the good polymer dielectric film of how simple technology obtained performance and the ionic conductivity, physical strength and the chemical property that further improve polymer dielectric film have significance to the development of polymer Li-ion battery and hull cell.
Summary of the invention
The object of the invention aims to provide a kind of simple, practical, is easy to the preparation method of porousness composite polymer electrolyte membrane of the lithium ion battery of industrial applications; Polymer dielectric film through method gained of the present invention has abundant, proper pore structure, has reduced crystallinity of polymer, quite high porosity, thus greatly improved the ionic conductivity of polymeric film, and have good electrochemical stability window.
Technical scheme of the present invention is following:
Ammonium salt solution, nano inorganic are added particle join the organic solvent vibration evenly; Add in pvdf (PVDF), vinylidene and the hexafluoropropylene copolymer (PVDF-HFP) one or both then, wherein ammonium salt: nano inorganic particle: pvdf: vinylidene and hexafluoropropylene copolymer: the mass ratio of the adding of organic solvent is 0.1～0.3:0.05～0.3:x:1-x:3～6 (1 >=x >=0); Said mixture obtains even gel 10-30 ℃ of stirring, leaves standstill the removal bubble; Gel evenly is coated on the sheet glass, and the film forming while of solvent flashing in 40-90 ℃ of air or under the vacuum condition, ammonium salt is broken down into water, ammonia and blown with carbon dioxide pore-creating and obtains polymer electrolyte film.
The resulting polymers electrolytic thin-membrane shows good electrochemical after the lithium salt solution of EC-DMC-EMC soaks activation, plasticising.
Above-mentioned ammonium salt is NH
4HCO
3, (NH
4)
2CO
3, NH
2COONH
4In one or more.
The mass percent concentration of ammonium salt solution is preferably 2-8%, most preferably is 2.5-5%.
It is Al that nano inorganic adds particle
2O
3, TiO
2, SiO
2, MgO, ZrO
2, AlBr
3, BaTiO
3In one or more.
Organic solvent is a N,N-DIMETHYLACETAMIDE, acetone, N-Methyl pyrrolidone, one or more in the N.
Said mixture is preferably 1-5h in the time of 10-30 ℃ of stirring.Should guarantee that the time of stirring is suitable mutually with temperature, decompose in a large number to avoid ammonium salt.
Compare with prior art, the present invention has the following advantages:
(1) compares with traditional porous polymer electrolyte; Thermolysis Cheng Shui, ammonia and carbonic acid gas squeeze film-casting liquid in the ammonium salt drying courses such as bicarbonate of ammonia in the polymer electrolyte film among the present invention; Make dielectric film in solidification process, form micropore; Thereby promote the porosity of dielectric film, strengthened the electrolyte ion specific conductivity.This has just solved in the past the direct solvent volatilization method, and to produce dielectric film pore-creating difficult, and porosity is low, the problem that specific conductivity is low.And the contriver finds directly to adopt the words of ammonium salt when R&D process technical scheme of the present invention; Difficulty is dissolved in organic solvent with ammonium salt; Join in the film-casting liquid and can't obtain even colloid; In order to solve this difficult point, after being made into ammonium salt the aqueous solution, join in the film-casting liquid in this programme, obtain clarifying colloid.In addition, the present invention cooperates solvent evaporation method to add nanometer Al
2O
3When make simplifying technology, abundant, proper pore structure (seeing Fig. 1, table 1) that the resulting polymers film has has improved the ionic conduction ability of polymeric film.
(2) compare with traditional porous polymer electrolyte; The moisture that polymer electrolyte film among the present invention prepares in the ammonium salt solution in the process can be accelerated film process mesosome curing speed just; Thereby reduce crystallinity of polymer (seeing table 1), improve ionic conductivity.
(3) compare with traditional porous polymer electrolyte; The shortcoming that polymer electrolyte film preparation method among the present invention has avoided traditional phase transfer method preparation method to cause the dielectric film mechanical performance sharply to descend, the probability that makes dendrite in the lithium ion battery charge and discharge process pierce through dielectric film reduces greatly; Simultaneously, guarantee that dielectric film has quite high porosity (seeing Table 1) and ionic conductivity.
Table 1 is the prepared typical PVDF/Al of the present invention
2O
3Polymer electrolyte film and conventional gas-phase volatilization method prepare the porosity of film, the contrast of percent crystallinity.
| Scheme | Percent crystallinity/% | Porosity/% |
| The present invention program | 18%～36% | 50%～70% |
| Traditional scheme | 30%～50% | 20%～30% |
In sum, but method of the present invention fully is to utilize under the low temperature thermolysis to carry out pore-creating, combine solvent evaporates and add inorganic nano particle modified mode for gaseous compound, and preparation is like PVDF-HFP/Al
2O
3, PVDF/Al
2O
3And PVDF-HFP/PVDF/Al
2O
3At interior composite polymer electrolyte film, making polymer dielectric film has better ionic conductivity and physical strength, and has the electrochemical stability window of broad, thereby satisfies the needs of film lithium ion battery, and technology is simple, is easy to industriallization.
Description of drawings
Fig. 1 is the prepared typical PVDF/Al of the present invention
2O
3The SEM figure of polymer electrolyte film.
Embodiment
Below in conjunction with specific embodiment the present invention is done and to further describe.The present invention can implement by arbitrary mode of summary of the invention.Providing of these embodiment limits the present invention anything but.
Embodiment 1
With amount of ammonium bicarbonate solution (W
NH4HCO3=5%) nanometer Al,
2O
3Join N,N-DIMETHYLACETAMIDE (DMAC) vibration evenly, add pvdf (PVDF) then, wherein NH
4HCO
3: Al
2O
3: the mass ratio of PVDF:DMAC is 0.1:0.05:1:6; Stir 2h at 30 ℃, obtain even gel, leave standstill the removal bubble, gel evenly is coated on the sheet glass,, obtain the PVDF/Al that bicarbonate of ammonia is decomposed into water, ammonia and carbonic acid gas pore-creating modification 80 ℃ of following solvent flashing film forming
2O
3Polymer electrolyte film.
Gained PVDF/Al
2O
3Polymer electrolyte film is through 1mol/L LiPF
6The activation of EC-DMC-EMC solution soaking after, adopting its ionic conductivity of alternating-current impedance method test is 2.3mS/cm.The cyclic voltammetry test shows, PVDF/Al
2O
3Electrochemical stability window＞the 5.5V of electrolytic thin-membrane, breaking tenacity＞15MPa, porosity is 57%.
Embodiment 2
With an amount of sal volatile (W
(NH4) 2CO3=2.5%) nanometer SiO,
2Join N (DMF) vibration evenly, add pvdf (PVDF) then, wherein (NH
4)
2CO
3: SiO
2: the PVDF:DMF proportioning is 0.3:0.3:1:4; Stir 2h at 15 ℃, obtain even gel, leave standstill the removal bubble, gel evenly is coated on the sheet glass,, obtain the PVDF/SiO that volatile salt is decomposed into water, ammonia and carbonic acid gas pore-creating modification 90 ℃ of following solvent flashing film forming
2Polymer electrolyte film.
Gained PVDF/SiO
2Polymer electrolyte film is through 1mol/L LiPF
6The activation of EC-DMC-EMC solution soaking, plasticising after, adopting its ionic conductivity of alternating-current impedance method test is 2.4mS/cm.The cyclic voltammetry test shows, PVDF/SiO
2Electrochemical stability window＞the 5.5V of electrolytic thin-membrane, breaking tenacity＞22MPa, porosity is 60%.
Embodiment 3
With an amount of ammonium carbamate solution (W
NH2COONH4=5%) nano-TiO,
2Join the acetone vibration evenly, add hexafluoropropylene copolymer (PVDF-HFP) then, wherein NH
2COONH
4: TiO
2: PVDF-HFP: the acetone proportioning is 0.1:0.1:1:5; Stir 5h at 10 ℃, obtain even gel, leave standstill the removal bubble, gel evenly is coated on the sheet glass, solvent flashing film forming under 90 ℃ of vacuum conditions obtains the PVDF-HFP/TiO that ammonium carbamate is decomposed into ammonia and carbonic acid gas pore-creating modification
2Polymer electrolyte film.
Gained PVDF-HFP/TiO
2Polymer electrolyte film is through 1mol/L LiPF
6The activation of EC-DMC-EMC solution soaking, plasticising after, adopting its ionic conductivity of alternating-current impedance method test is 2.8mS/cm.The cyclic voltammetry test shows, PVDF-HFP/TiO
2Electrochemical stability window＞the 5.5V of electrolytic thin-membrane, breaking tenacity＞11MPa, porosity is 65%.
Embodiment 4
With amount of ammonium bicarbonate solution (W
NH4HCO3=5%) nanometer Al,
2O
3Join N-Methyl pyrrolidone (NMP) vibration evenly, add vinylidene and hexafluoropropylene copolymer (PVDF-HFP) and pvdf (PVDF) polymer blend, wherein NH then
4HCO
3: Al
2O
3: the PVDF-HFP:PVDF:NMP proportioning is 0.1:0.1:0.5:0.5:6; Stir 2h at 25 ℃, obtain even gel, leave standstill the removal bubble, gel evenly is coated on the sheet glass, solvent flashing film forming under 40 ℃ of vacuum conditions obtains the PVDF-HFP/PVDF/Al that bicarbonate of ammonia is decomposed into ammonia and carbonic acid gas pore-creating modification
2O
3Polymer electrolyte film.
Gained PVDF-HFP/PVDF/Al
2O
3Polymer electrolyte film is through 1mol/L LiPF
6The activation of EC-DMC-EMC solution soaking, plasticising after, adopting its ionic conductivity of alternating-current impedance method test is 3.1mS/cm.The cyclic voltammetry test shows, PVDF-HFP/PVDF/Al
2O
3Electrochemical stability window＞the 5.5V of electrolytic thin-membrane, breaking tenacity＞13MPa, porosity is 68%.
Claims (6)
1. a gas phase is volatilized and is prepared the method for porous polymer electrolytic thin-membrane, it is characterized in that, ammonium salt solution, nano inorganic particle are joined in the organic solvent and mix; Add in pvdf, vinylidene and the hexafluoropropylene copolymer one or both then; Said mixture obtains even gel 10-30 ℃ of stirring, leaves standstill the removal bubble; Evenly be coated on gel on the sheet glass; The film forming while of solvent flashing in 40-90 ℃ of air or under the vacuum condition, ammonium salt decomposes the ammonia, carbonic acid gas, the water that produce and squeezes film-casting liquid and form hole, obtains the porous polymer electrolytic thin-membrane; Ammonium salt: nano inorganic particle: pvdf: vinylidene and hexafluoropropylene copolymer: the mass ratio of organic solvent is 0.1～0.3:0.05～0.3:x:1-x:3～6; 1>=x>=0 wherein; Said ammonium salt is NH
4HCO
3, (NH
4)
2CO
3, NH
2COONH
4In one or more.
2. method according to claim 1, its characteristic are that the mass percent concentration of ammonium salt solution is 2-8%.
3. method according to claim 2, its characteristic are that the mass percent concentration of ammonium salt solution is 2.5-5%.
4. method according to claim 1, its characteristic are that it is Al that said nano inorganic adds particle
2O
3, TiO
2, SiO
2, MgO, ZrO
2, AlBr
3, BaTiO
3In one or more;
5. method according to claim 1, its characteristic are that said organic solvent is a N,N-DIMETHYLACETAMIDE, acetone, N-Methyl pyrrolidone, one or more in the N.
6. method according to claim 1, its characteristic are that mixture is 1-5h 10-30 ℃ of time of stirring down.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102617881B (en) * | 2012-04-10 | 2013-07-17 | 中南大学 | Preparation method of porous gel polymer lithium ion battery diaphragm |
| CN103840199A (en) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | PEO (Polyoxyethylene)-based gel polymer electrolyte membrane, preparation method of membrane, and lithium ion battery |
| CN103840109A (en) * | 2012-11-26 | 2014-06-04 | 海洋王照明科技股份有限公司 | Polyvinyl-acetate-based gel polymer electrolyte membrane, preparation method of membrane, and lithium-ion battery |
| CN103746142B (en) * | 2013-12-20 | 2017-02-22 | 厦门首能科技有限公司 | Gel electrolyte for lithium ion secondary battery and preparation method of gel electrolyte |
| CN105301068A (en) * | 2015-09-22 | 2016-02-03 | 国家电网公司 | Preparation method of gel electrolyte for electrochemical oxygen alarming device |
| CN110600797A (en) * | 2019-09-29 | 2019-12-20 | 天津空间电源科技有限公司 | Preparation method of polymer-inorganic composite electrolyte |
| CN112652797B (en) * | 2019-10-11 | 2022-03-08 | 中国科学院大连化学物理研究所 | Porous ion-conducting membrane with pore size in gradient distribution, preparation and application |
| CN111672338A (en) * | 2020-05-18 | 2020-09-18 | 浙江格尔泰斯环保特材科技股份有限公司 | Preparation method of polytetrafluoroethylene microporous film with ultrahigh porosity |
| CN113043620B (en) * | 2021-03-29 | 2024-06-07 | 浙江格尔泰斯环保特材科技股份有限公司 | Preparation method of polytetrafluoroethylene film with ultrahigh air permeability |
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