CN1916069A - Method for preparing electrolyte of porous compound polymer doped by titanium dioxide through hydrolysis method in situ - Google Patents

Method for preparing electrolyte of porous compound polymer doped by titanium dioxide through hydrolysis method in situ Download PDF

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Publication number
CN1916069A
CN1916069A CNA2006101125940A CN200610112594A CN1916069A CN 1916069 A CN1916069 A CN 1916069A CN A2006101125940 A CNA2006101125940 A CN A2006101125940A CN 200610112594 A CN200610112594 A CN 200610112594A CN 1916069 A CN1916069 A CN 1916069A
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tetrabutyl titanate
film
solution
titanium dioxide
compound polymer
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CN100365056C (en
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王新东
刘伯文
朱中正
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University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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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
    • 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
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    • Y02E60/10—Energy storage using batteries

Abstract

This invention relates to an in-situ hydrolysis method for preparing TiO2-doped porous composite polymer electrolyte for Li-ion batteries. The method comprises: (1) dropping diluted tetrabutyl titanate (TBT) solution into mixed acetone solution under stirring to obtain white TiO2 sol; (2) adding PVDF-HFP and n-butanol into white TiO2 sol, heating to 40-60 deg.C and stirring for 2-4 h; (3) preparing TiO2-doped porous composite polymer membrane, and immersing in Li-ion battery electrolytic solution to obtain ion-conductive electrolyte membrane. The method improves the porous network strcture of the electrolyte membrane, and TiO2 is uniformly distributed without forming aggregates. Besides, TiO2 is closely linked with the polymer matrix, thus improving the electrochemical and mechanical properties of the electrolyte membrane.

Description

A kind of method for preparing electrolyte of porous compound polymer of doped by titanium dioxide through hydrolysis method in situ
Technical field
The present invention relates to method for preparing polymer electrolytes, specially refer to the preparation of polymer lithium ion battery electrolyte.
Background technology
Polymer dielectric film is the key material of polymer Li-ion battery, as the barrier film and the ionogen of lithium ion battery, polymer dielectric film should possess characteristics such as the electrochemical window of higher room-temperature ion electric conductivity, good electrode interface stability, broad and favorable mechanical performance.At present, polymer dielectric can be divided into three types by structural form: pure solid polymer electrolyte (DSPE), gel-type polymer electrolyte (GSPE) and porous polymer ionogen (PSPE).The electrolytical ionic conductivity of DSPE is lower, and maximum is 10 -5～10 -4Scm -1The order of magnitude can not satisfy the requirement of lithium ion battery.Two kinds of electrolytical ionic conductivities of GSPE and PSPE all can reach 10 -3Scm -1More than the order of magnitude, but its mechanical property but can not be satisfactory.Strengthen theory according to macromolecular material, in macromolecular material, add some inorganic materials, can effectively strengthen the mechanical property of macromolecular material.Studies show that, in polymer electrolyte matrices, mix a spot of small size inorganic powder material and both can improve its physical strength effectively, can improve again ionic conductivity and with the stability of electrode interface.The 121st～131 page of " Characterization ofpoly (vinylidenefluoride-co-hexafiuoropropylene)-based polymer electrolyte filledwith rutile TiO that delivers of " Solid State Ionics " 2003 the 161st volumes 2Nanoparticles " in the article, with nano-TiO 2Powder adds vinylidene fluoride-hexafluoropropylene copolymer/LiPF to 6In the system, find that inorganic particulate helps the dispersion and the disassociation of salt, its specific conductivity is increased; Employing extraction process preparation interpolation nanometer Al reported in the article of " electroconductibility of nano-filled PVDF-HFP composite electrolyte " in " SCI " 2003 the 24th volumes o. 11th 2O 3PVDF-HFP base electrolyte film, the ionic conductivity of this film reaches 1.7mScm -1But because these two kinds of methods all adopt is that inorganic nanometer powder is made weighting agent, and the surfactivity height of nano-powder material is difficult for disperseing, and causes the ununiformity of dielectric film, thereby has influenced the performance of composite electrolyte membrane.
Summary of the invention
The present invention proposes to realize the inorganic nano material of polymer dielectric is mixed by the in-situ hydrolysis method, adopt phase inversion process to prepare polyvinylidene difluoride (PVDF)-hexafluoropropylene copolymer (PVDF-HFP) based composite electrolyte film, improve the porous network structure of dielectric film, solve the agglomeration traits of titanium dioxide granule, not only can improve the homogeneity of composite electrolyte membrane, and titanium dioxide is tight with combining of polymeric matrix, composite effect is good, thereby improves the chemical property and the stability of multi-hole type composite electrolyte membrane.
Implementation step of the present invention is:
(1) preparation tetrabutyl titanate diluent is dissolved in tetrabutyl titanate in the tetrahydrofuran (THF), and being mixed with concentration is the tetrabutyl titanate yellow solution of 0.04～0.15 grams per milliliter;
(2) preparation acetone mixed solution, high purity water, hydrochloric acid and acetone mixing are obtained clear solution, the mol ratio that makes tetrabutyl titanate and water is a tetrabutyl titanate: water=0.01～0.1, the pH value of hydrochloric acid conditioning solution is 1.5～2.5, by weight percentage, PVDF-HFP: acetone=1: 5～1: 15;
(3) preparation TiO 2Colloidal sol under 20～25 ℃, is added drop-wise to the tetrabutyl titanate diluent in the acetone mixed solution of stirring, obtains TiO 2Leucosol;
(4) prepare compound film-casting liquid, PVDF-HFP and propyl carbinol are joined TiO 2In the leucosol, be warmed up to 40～60 ℃, constant temperature stirs 2～4h, by weight percentage, makes PVDF-HFP: propyl carbinol: TiO 2=1: 1～5: 0.03～0.2;
(5) system film, treat that polymkeric substance fully dissolves after, be cooled to 25～30 ℃ while stirring, this oyster white film-casting liquid is cast in the forming mould, treat solvent and non-solvent the volatilization after obtain the adulterated white porous compound polymer film of titanium dioxide;
(6) activation is under dry environment, with the porous compound polymer film immersion after the vacuum-drying in the electrolytic solution of lithium ion battery 30～60 minutes.Take out and inhale the electrolytic solution that goes to the surface unnecessary, obtain having the composite electrolyte membrane of ionic conducting property.
Consisting of of electrolytic solution: phosphofluoric acid lithium salts (LiPF 6) be dissolved in the mixing solutions of NSC 11801 (EC) and methylcarbonate (DMC) LiPF wherein 6Concentration be 1 mol, the weight ratio of EC and DMC is 1: 1.
Compared with prior art, characteristics of the present invention are:
Realize the inorganic materials of polymer dielectric is mixed by the in-situ hydrolysis method, adopt phase inversion process to prepare titanium dioxide doped P VDF-HFP (model LBG-1) based composite electrolyte film.Adopt the in-situ hydrolysis polycondensation to generate titanium dioxide, inorganic materials is disperseed very even, and titanium dioxide is tight with combining of polymeric matrix, and composite effect is good, and therefore the chemical property of prepared multi-hole type composite electrolyte membrane is significantly improved.The ionic conductivity of blank assay sample dielectric film is 3.62 * 10 -4Scm -1, behind the doped by titanium dioxide through hydrolysis method in situ, the ionic conductivity of composite electrolyte obviously improves, 1～2 * 10 -3Scm -1About.
Fig. 1 is the surperficial SEM photo of blank assay porous polymer membrane sample, and Fig. 2 is in-situ hydrolysis method doped Ti O 2The surperficial SEM photo of porous compound polymer membrane sample.From Fig. 1 and Fig. 2 as can be seen: the network skeleton thickness of apertured polymeric film is inhomogeneous Fig. 1, and the physical strength of this network skeleton structure is relatively poor; In-situ hydrolysis doped Ti O among Fig. 2 2The network skeleton structure of porous composite electrolyte membrane more even, the specific surface area of film is very big, this structure helps absorption and the maintenance of apertured polymeric film to electrolytic solution, thereby improves the ionic conductivity of dielectric film.
Description of drawings
Fig. 1 makes the SEM figure of sample for blank assay
Fig. 2 makes the SEM figure of sample for embodiment 1
Fig. 3 makes the SEM figure of sample for embodiment 3
Embodiment
Embodiment 1:
(1) preparation tetrabutyl titanate diluent, the tetrabutyl titanate that takes by weighing 0.141g is dissolved in the 1ml tetrahydrofuran (THF), obtains yellow solution;
(2) preparation acetone mixed solution obtains clear solution with 0.2g high purity water, 0.05g 37% concentrated hydrochloric acid and the mixing of 7.5ml acetone;
(3) preparation TiO 2Colloidal sol under 20 ℃, is added drop-wise to the tetrabutyl titanate diluent in the acetone mixed solution of stirring, obtains TiO 2Leucosol;
(4) prepare compound film-casting liquid, 0.5g PVDF-HFP and 1.24ml propyl carbinol are joined TiO 2In the leucosol, be warmed up to 50 ℃, constant temperature stirs 3h;
(5) system film, treat that polymkeric substance fully dissolves after, be cooled to 30 ℃ while stirring, this oyster white film-casting liquid is cast in the forming mould, treat solvent and non-solvent the volatilization after obtain the adulterated white porous compound polymer film of titanium dioxide;
(6) activation is under dry environment, with the porous compound polymer film immersion after the vacuum-drying in the electrolytic solution of lithium ion battery 35 minutes.Consisting of of electrolytic solution: phosphofluoric acid lithium salts (LiPF 6) dissolving is in the mixing solutions of NSC 11801 (EC) and methylcarbonate (DMC) LiPF wherein 6Concentration be 1 mol, the weight ratio of EC and DMC is 1: 1.Take out and inhale the electrolytic solution that goes to the surface unnecessary, obtain having the composite electrolyte membrane of ionic conducting property.
The SEM microcosmic picture of the porous compound polymer film that embodiment 1 makes is seen Fig. 2.As can be seen from the figure: adopt in-situ hydrolysis method doped Ti O 2The microtexture of porous compound polymer film more even, specific surface area is very big, network skeleton is thinner and even, TiO 2Combine together with polymeric matrix, this structure not only helps absorption and the maintenance of porous compound polymer film to electrolytic solution, thereby improve the ionic conductivity of dielectric film, the homogeneity of polymer backbone will significantly improve the mechanical property of composite electrolyte membrane simultaneously.The ionic conductivity of the porous composite electrolyte membrane that embodiment 1 makes can reach 1.75 * 10 -3Scm -1
Embodiment 2:
(1) preparation tetrabutyl titanate diluent, the tetrabutyl titanate that takes by weighing 0.1128g is dissolved in the 1ml tetrahydrofuran (THF), obtains yellow solution;
(2) preparation acetone mixed solution obtains clear solution with 0.2g high purity water, 0.05g 37% concentrated hydrochloric acid and the mixing of 7.5ml acetone;
(3) preparation TiO 2Colloidal sol under 20 ℃, is added drop-wise to the tetrabutyl titanate diluent in the acetone mixed solution of stirring, obtains TiO 2Leucosol;
(4) prepare compound film-casting liquid, 0.5g PVDF-HFP and 1.24ml propyl carbinol are joined TiO 2In the leucosol, be warmed up to 50 ℃, constant temperature stirs 3h;
(5) system film, treat that polymkeric substance fully dissolves after, be cooled to 30 ℃ while stirring, this oyster white film-casting liquid is cast in the forming mould, treat solvent and non-solvent the volatilization after obtain the adulterated white porous compound polymer film of titanium dioxide;
(6) activation is under dry environment, with the porous compound polymer film immersion after the vacuum-drying in the electrolytic solution of lithium ion battery 50 minutes.Consisting of of electrolytic solution: phosphofluoric acid lithium salts (LiPF 6) dissolving is in the mixing solutions of NSC 11801 (EC) and methylcarbonate (DMC) LiPF wherein 6Concentration be 1 mol, the weight ratio of EC and DMC is 1: 1.Take out and inhale the electrolytic solution that goes to the surface unnecessary, obtain having the composite electrolyte membrane of ionic conducting property.
Embodiment 2 has made white uniform porous composite electrolyte membrane, and the ionic conductivity of this dielectric film can reach 2.1 * 10 -3Scm -1
Embodiment 3:
(1) preparation tetrabutyl titanate diluent, the tetrabutyl titanate that takes by weighing 0.0846g is dissolved in the 1ml tetrahydrofuran (THF), obtains yellow solution;
Preparation acetone mixed solution obtains clear solution with 0.15g high purity water, 0.05g 37% concentrated hydrochloric acid and the mixing of 6ml acetone;
(2) preparation TiO 2Colloidal sol under 20 ℃, is added drop-wise to the tetrabutyl titanate diluent in the acetone mixed solution of stirring, obtains TiO 2Leucosol;
(3) prepare compound film-casting liquid, 0.5g PVDF-HFP and 0.925ml propyl carbinol are joined TiO 2In the leucosol, be warmed up to 50 ℃, constant temperature stirs 3h;
(4) system film, treat that polymkeric substance fully dissolves after, be cooled to 30 ℃ while stirring, this oyster white film-casting liquid is cast in the forming mould, treat solvent and non-solvent the volatilization after obtain the adulterated white porous compound polymer film of titanium dioxide;
(5) activation is under dry environment, with the porous compound polymer film immersion after the vacuum-drying in the electrolytic solution of lithium ion battery 55 minutes.Consisting of of electrolytic solution: phosphofluoric acid lithium salts (LiPF 6) dissolving is in the mixing solutions of NSC 11801 (EC) and methylcarbonate (DMC) LiPF wherein 6Concentration be 1 mol, the weight ratio of EC and DMC is 1: 1.Take out and inhale the electrolytic solution that goes to the surface unnecessary, obtain having the composite electrolyte membrane of ionic conducting property.
The SEM microcosmic picture of the porous compound polymer film that embodiment 3 makes is seen Fig. 3.As can be seen from Figure 3: adopt in-situ hydrolysis method doped Ti O 2The microtexture of porous compound polymer film more even, specific surface area is very big, network skeleton is thinner and even, TiO 2Combine together with polymeric matrix.This structure not only helps absorption and the maintenance of porous compound polymer film to electrolytic solution, thereby improves the ionic conductivity of dielectric film, and the homogeneity of polymer backbone will significantly improve the mechanical property of composite electrolyte membrane simultaneously.The ionic conductivity of the porous composite electrolyte membrane that embodiment 3 makes can reach 1.46 * 10 -3Scm -1

Claims (2)

1, a kind of method for preparing electrolyte of porous compound polymer of doped by titanium dioxide through hydrolysis method in situ is characterized in that, implementation step of the present invention is:
1) preparation tetrabutyl titanate diluent is dissolved in tetrabutyl titanate in the tetrahydrofuran (THF), and being mixed with concentration is the tetrabutyl titanate yellow solution of 0.04～0.15 grams per milliliter;
2) preparation acetone mixed solution, high purity water, hydrochloric acid and acetone mixing are obtained clear solution, and the mol ratio that makes tetrabutyl titanate and water is a tetrabutyl titanate: water=0.01～0.1, and the pH value of hydrochloric acid conditioning solution is 1.5～2.5, by weight percentage, PVDF-HFP: acetone=1: 5～1: 15;
3) preparation TiO 2Colloidal sol under 20～25 ℃, is added drop-wise to the tetrabutyl titanate diluent in the acetone mixed solution of stirring, obtains TiO 2Leucosol;
4) prepare compound film-casting liquid, PVDF-HFP and propyl carbinol are joined TiO 2In the leucosol, be warmed up to 40～60 ℃, constant temperature stirs 2～4h, by weight percentage, makes PVDF-HFP: propyl carbinol: TiO 2=1: 1～5: 0.03～0.2;
5) system film, treat that polymkeric substance fully dissolves after, be cooled to 25～30 ℃ while stirring, this oyster white film-casting liquid is cast in the forming mould, treat solvent and non-solvent the volatilization after obtain the adulterated white porous compound polymer film of titanium dioxide;
6) activation is under dry environment, with the porous compound polymer film immersion after the vacuum-drying in the electrolytic solution of lithium ion battery 30～60 minutes.Take out and inhale the electrolytic solution that goes to the surface unnecessary, obtain having the composite electrolyte membrane of ionic conducting property.
2, the method for preparing electrolyte of porous compound polymer of doped by titanium dioxide through hydrolysis method in situ as claimed in claim 1 is characterized in that, the consisting of of the electrolytic solution of lithium ion battery: phosphofluoric acid lithium salts LiPF 6Be dissolved in the mixing solutions of NSC 11801 EC and methylcarbonate DMC, wherein LiPF 6Concentration be 1 mol, the weight ratio of EC and DMC is 1: 1.
CNB2006101125940A 2006-08-24 2006-08-24 Method for preparing electrolyte of porous compound polymer doped by titanium dioxide through hydrolysis method in situ Expired - Fee Related CN100365056C (en)

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CN100519635C (en) * 2007-04-12 2009-07-29 中国科学院长春应用化学研究所 Beta phase polyvinylidene fluoride composite film and preparation method thereof
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CN104600358A (en) * 2015-01-21 2015-05-06 长沙宝锋能源科技有限公司 All-solid-state polymer electrolyte for surface chemical grafting inorganic particles and preparation method of all-solid-state polymer electrolyte
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