CN103560220A - Method for preparing lithium ion battery polymer gel electrolyte membrane - Google Patents

Method for preparing lithium ion battery polymer gel electrolyte membrane Download PDF

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Publication number
CN103560220A
CN103560220A CN201310556913.7A CN201310556913A CN103560220A CN 103560220 A CN103560220 A CN 103560220A CN 201310556913 A CN201310556913 A CN 201310556913A CN 103560220 A CN103560220 A CN 103560220A
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substrate
mixture
lithium
spraying
gel electrolyte
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Chinese (zh)
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向勇
郁嘉文
张庶
臧亮
张晓琨
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
    • B05B13/00—Machines or plants for applying liquids or other fluent materials to surfaces of objects or other work by spraying, not covered by groups B05B1/00 - B05B11/00
    • B05B13/02—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work
    • B05B13/04—Means for supporting work; Arrangement or mounting of spray heads; Adaptation or arrangement of means for feeding work the spray heads being moved during spraying operation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • 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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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a method for preparing a lithium ion battery polymer gel electrolyte membrane. The method is characterized in that a polymer membrane assembly solution of gel electrolyte is sprayed and coated on a substrate through a spray coating method and is dried in situ. The method specifically comprises the following steps: 1) preparing a matrix polymer mixture, an anionic surfactant, a non-proton solvent system and phase separation liquid; 2) mixing the mixture, the anionic surfactant, the non-proton solvent system and the phase separation liquid prepared in the step 1) to form a liquid phase mixture; 3) adding a lithium electrolyte salt in the mixture to prepare a mixed solution; and 4) spraying and coating the mixed solution prepared in the step 3) on a pole piece on the substrate, and carrying out in situ drying on the substrate to prepare the lithium ion battery polymer gel electrolyte membrane. The liquid phase spray coating-in situ drying technology is used for reducing the movement of material components to be cured to form a skeleton structure and material components used for forming the gel electrolyte on the substrate, and the formed porous structures are uniformly distributed.

Description

A kind of preparation method of lithium ion battery polymer gel electrolyte barrier film
Technical field
The invention belongs to technical field of lithium-ion battery, especially relate to a kind of preparation method of lithium ion battery polymer gel electrolyte barrier film.
Background technology
Solid-state/gel/poly-lithium battery has used novel polymer lithium battery diaphragm and electrolyte assembly (containing the polymer lithium cell diaphragm of gel electrolyte), combine the advantage of old-fashioned liquid phase and solid phase lithium battery, adopt the foamed polymer of solid phase as barrier film matrix, and by gel state material on the space wall of resident foam barrier film as electrolyte, even if container breaks like this, electrolyte still can reside in battery.Make solid state lithium battery in shape, size, weight, liquid phase and solid phase lithium battery that fail safe and capacity aspect are more old-fashioned are greatly improved.
At present, for new polymers barrier film lithium battery, relatively the tape casting that has of main flow is prepared the scheme of barrier film (Thomas Lin et al, US2008066297A1).This technology be prepare at present that lithium battery adopts mainstream technology.But this method and to lift barrier film prepared by the coating method performance in the homogeneity of uniform thickness and loose structure not good enough, adopts the lithium ion battery of gel-form solid polymer electrolyte technology with market, to realize scale volume production upper thereby restricted.Intaglio plate coating, reverse roll coating, slope flow coat cloth or extrusion coated (China Patent Publication No. CN 101420019A) easily cause polymer molecular chain long slack time, and crystalline region crystallization is perfect, conductivity reduces.
Summary of the invention
The preparation method who the object of the invention is to propose a kind of gel polymer electrolyte barrier film based on " liquid phase spraying-dried in place " (substrate being dried in the original place, position of spraying substrate) solves current lithium battery diaphragm production septation caused cost in uneven thickness, battery performance, and safety problem.
The technical solution adopted in the present invention is as follows:
A preparation method for lithium ion battery polymer gel electrolyte barrier film, the method is sprayed at the membrane for polymer assembly soln using spraying method of gel electrolyte in substrate, to carry out dried in place; Its concrete steps comprise:
1) prepare matrix polymer mixture, anion surfactant, aprotic solvent system and the liquid that is separated;
2) by step 1) polymeric blends, surfactant, the aprotic solvent system prepared and be separated liquid in mass ratio 1:2-4:8-10:2-3 be mixed to form liquid phase mixture;
3) in mixture, adding lithium electrolyte salt to be mixed to get lithium concentration is 0.8～1.5mol/L mixed liquor;
4) utilize mixed liquor that spraying method is prepared step 3) to be sprayed at and be positioned at suprabasil pole piece, in substrate, carry out after dried in place.
The inventive method step also comprises: repeating step 4) increase dielectric film thickness.
Described matrix polymer mixture is mixing quality than mixing for the polyvinyl fluoride of 1:0.08-0.5 and polystyrene.
Described surfactant is 10-30% toluenesulfonic acid lithium solution for take the mass fraction that ether and acetone mixed solution be solvent; The mixing quality of ether and acetone is than being 1-3:1
Described aprotic solvent system is that mass ratio is the mixture of the dimethyl carbonate of 5:4:6:100-200, different propylene, ethylene carbonate and oxolane.
The described solution that is separated is one or more arbitrary proportion mixed solutions of hexane, toluene, benzene or tetrachloromethane.
Lithium-ion electrolyte salt described in step 3) is lithium hexafluoro phosphate, LiClO 4, LiASF 6, LiBF 4, LiAlCl 4, CH 3sO 3li, CF 3sO 3a kind of or its any mixture of Li; In described mixed liquor, lithium concentration is 0.8～1.5mol/L;
Described spraying method, wherein the scope of spraying is substrate, and path adopts Z-shaped round about manner, sprays and is set as 5-15 minute interval time, and shower nozzle translational speed is 0.5-2mm/s, and needle tubing flow is 0.5-2mL/min; The vertical range of shower nozzle and substrate superior pole piece is 15-30cm.
Described substrate dried in place temperature is 50-70 ℃.
The invention still further relates to a kind of dried in place spraying equipment for the preparation of lithium ion battery polymer gel electrolyte barrier film, comprise spraying substrate, for heating heating plate, shower nozzle and the removable mechanical arm of substrate; Described heating plate one end is provided with the concavo-convex draw-in groove chimeric with removable mechanical arm, and shower nozzle is placed in the removable mechanical arm other end, on the suprabasil pole piece of described shower nozzle spraying mixt under it; Substrate is placed on heating plate.
The technique of this by repeating " liquid phase spraying-dried in place ", makes membrane thicknesses and structure all reach expection requirement; Apply this " liquid phase spraying-dried in place " technology, reduced in order to solidify to form the material component of skeleton structure and in order to the material component that forms gel electrolyte in on-chip movement, the pore structure forming is evenly distributed in barrier film, in the same size, be conducive to keep the homogeneity of liquid phase coating, thereby improve the performance of lithium battery.What make preparation has high conductivity containing the polymer Li-ion battery of gel electrolyte, thermal stability, chemical stability, and stronger mechanical performance and use dried in place greatly to enhance productivity.Service routine is controlled the barrier film that spray gun more can one-shot forming required form, has effectively saved sprayed on material, reduces costs.
Accompanying drawing explanation
Fig. 1 is the gel-form solid polymer electrolyte film electron scanning micrograph shown in embodiment 1;
Fig. 2 is the electron micrograph of the gel-form solid polymer electrolyte film loose structure described in embodiment 1;
Fig. 3: dried in place spraying equipment vertical view;
Fig. 4: dried in place spraying equipment lateral plan;
Fig. 5: dried in place spraying equipment front view.
Embodiment
The present invention is further illustrated with accompanying drawing in conjunction with the embodiments.
Embodiment 1
As accompanying drawing 3,4, the spraying equipment of dried in place shown in 5, comprise spraying substrate 1002, for heating heating plate 1001, shower nozzle 1003 and the removable mechanical arm 1004 of substrate; Described heating plate 1001 one end are provided with the concavo-convex draw-in groove 1005 chimeric with removable mechanical arm, and shower nozzle 1003 is placed in removable mechanical arm 1004 other ends, shower nozzle 1003 be positioned at substrate 1002 directly over; Substrate 1002 is placed on heating plate 1001.
Embodiment 2
1) for the preparation of the matrix polymer mixture that forms micro-compound porous structure.This polymeric blends is that mass ratio is the polyvinyl fluoride of 1:0.08 and the mixture of polystyrene.
2), for the preparation of dissolve polymer aprotic solvent, this aprotic solvent is that mass ratio is the mixture of the carbonic acid dimethyl carbonate of 5:4:6:180, different propylene, ethylene carbonate and oxolane.
3) for the preparation of the anion surfactant of stablizing described gel phase.This surfactant is that mass fraction is ether and the acetone mixed solution of 20% toluenesulfonic acid lithium, and the mass ratio of ether and acetone is 3:1.
4) prepare a kind of liquid that is separated.This liquid that is separated is hexane, toluene, benzene arbitrary proportion mixing material formation.
5) by described blend polymer, described surfactant, described aprotic solvent system, described in the liquid that is separated mix the liquid phase mixture of formation, mixed proportion is 1:2:10:3, and add and make ionic transfer pass the electrolytic salt of micron composite structure q.s in described liquid phase mixture, lithium electrolyte salt consumption used is set according to final lithium concentration, stirs 3h.Described lithium-ion electrolyte salt is lithium hexafluoro phosphate, and after mixing, lithium concentration is 1mol/L.
5), under room temperature, the mixed liquor 10mL configuring is placed in to needle tubing.Before using needle tubing, use acetone, alcohol, washed with de-ionized water spray gun internal structure and substrate and needle tubing.
6) utilize the dried in place spraying equipment described in embodiment 1, startup gun controls program, setting the scope that need to spray is that substrate and path adopt Z-shaped round about manner, sprays and is set as 10 minutes interval time, shower nozzle translational speed is 1mm/s, and needle tubing flow is 1mL/min.The vertical range of shower nozzle and substrate superior pole piece is 20cm.
7) use air pressure spray gun that this solution is sprayed on substrate equably.And in spraying process, use heating plate to make substrate remain on 60 ℃.
8) and liquid phase mixture cooling until substrate evaporation forms after porous membrane, just can repeating step (7), until film thickness reaches expection requirement.
The scanning electron microscopy of the present embodiment gel electrolyte membrane shown in 1 and 2 by reference to the accompanying drawings, film thickness is about 20um, even thickness.Pore size distribution is even, big or small homogeneous, and the conductance of gained film is greater than 5 milli Siemens/cm.
Embodiment 3
Be with embodiment 2 differences: polymeric blends is that mass ratio is polyvinyl fluoride and the polystyrene of 1:0.5, and aprotic solvent is that mass ratio is the mixture of the carbonic acid dimethyl carbonate of 5:4:6:100, different propylene, ethylene carbonate and oxolane; Surfactant is that mass ratio is ether and the acetone mixture of 1:1; The described solution that is separated is hexane; Lithium-ion electrolyte salt is LiClO 4, LiASF 6, LiBF 4, LiAlCl 4any mixture, mixed liquid phase mixture lithium concentration is 1mol/L; Startup gun controls program, setting the scope that need to spray is substrate, and path adopts Z-shaped round about manner, sprays and is set as 5 minutes interval time, and shower nozzle translational speed is 2mm/s, and needle tubing flow is 2mL/min.The vertical range of shower nozzle and substrate superior pole piece is 15cm.The conductance of gained film is greater than 5 milli Siemens/cm.
Embodiment 4
Be with embodiment 2 differences: polymeric blends is that mass ratio is polyvinyl fluoride and the polystyrene of 1:0.3, and aprotic solvent is that mass ratio is the mixture of the carbonic acid dimethyl carbonate of 5:4:6:200, different propylene, ethylene carbonate and oxolane; Surfactant is that mass fraction is ether and the acetone mixed solution of 10% toluenesulfonic acid lithium, and the mass ratio of ether and acetone is 2:1; The described solution that is separated is benzene or tetrachloromethane any mixture; Blend polymer, described surfactant, described aprotic solvent system, described in the forming predetermined liquids ratio that is separated be 1:4:8:2; Lithium-ion electrolyte salt is CH 3sO 3li, mixed liquid phase mixture lithium concentration is 0.8mol/L; Startup gun controls program, setting the scope that need to spray is substrate, and path adopts Z-shaped round about manner, sprays and is set as 15 minutes interval time, and shower nozzle translational speed is 0.5mm/s, and needle tubing flow is 0.5mL/min.The vertical range of shower nozzle and substrate superior pole piece is 30cm.The conductance of gained film is greater than 5 milli Siemens/cm.
Embodiment 5
Be with embodiment 2 differences: polymeric blends is that mass ratio is polyvinyl fluoride and the polystyrene of 1:0.2, and aprotic solvent is that mass ratio is the mixture of the carbonic acid dimethyl carbonate of 5:4:6:150, different propylene, ethylene carbonate and oxolane; Surfactant is that mass fraction is ether and the acetone mixed solution of 30% toluenesulfonic acid lithium, and the mass ratio of ether and acetone is 1:1; The described solution that is separated is toluene; Blend polymer, described surfactant, described aprotic solvent system, described in the forming predetermined liquids ratio that is separated be 1:3:9:2.5; Lithium-ion electrolyte salt is CH 3sO 3li, CF 3sO 3any mixture of Li, mixed liquid phase mixture lithium concentration is 1.2mol/L; Startup gun controls program, setting the scope that need to spray is substrate, and path adopts Z-shaped round about manner, sprays and is set as 12 minutes interval time, and shower nozzle translational speed is 1.5mm/s, and needle tubing flow is 1.5mL/min.The vertical range of shower nozzle and substrate superior pole piece is 30cm.The conductance of gained film is greater than 5 milli Siemens/cm.

Claims (10)

1. a preparation method for lithium ion battery polymer gel electrolyte barrier film, is characterized in that, the method is that the membrane for polymer assembly soln using spraying method of gel electrolyte is sprayed in substrate and carries out dried in place, and its concrete steps comprise:
1) prepare matrix polymer mixture, anion surfactant, aprotic solvent system and the liquid that is separated;
2) by step 1) matrix polymer mixture mixture, anion surfactant, the aprotic solvent system prepared and be separated liquid in mass ratio 1:2-4:8-10:2-3 be mixed to form liquid phase mixture;
3) in mixture, adding lithium electrolyte salt to be mixed to get lithium concentration is 0.8～1.5mol/L mixed liquor;
4) utilize mixed liquor that spraying method is prepared step 3) to be sprayed at and be positioned at suprabasil pole piece, in substrate, carry out, after dried in place, completing preparation.
2. the method for claim 1, is characterized in that: described method step also comprises: repeating step 4) increase electrolyte membrance thickness.
3. the method for claim 1, is characterized in that: described matrix polymer mixture is mixing quality than mixing for the polyvinyl fluoride of 1:0.08-0.5 and polystyrene.
4. the method for claim 1, is characterized in that: described surfactant is 10-30% toluenesulfonic acid lithium solution for take the mass fraction that ether and acetone mixed solution be solvent; Described ether and the mixing quality of acetone are than being 1-3:1.
5. the method for claim 1, is characterized in that: described aprotic solvent system is that mass ratio is the mixture of the dimethyl carbonate of 5:4:6:100-200, different propylene, ethylene carbonate and oxolane.
6. the method for claim 1, is characterized in that: the described solution that is separated is one or more arbitrary proportion mixing materials of hexane, toluene, benzene or tetrachloromethane.
7. the method for claim 1, is characterized in that: the lithium-ion electrolyte salt described in described step 3) is lithium hexafluoro phosphate, LiClO 4, LiASF 6, LiBF 4, LiAlCl 4, CH 3sO 3li, CF 3sO 3a kind of or its any mixture of Li.
8. the method for claim 1, is characterized in that: the spraying method described in step 4), and wherein the scope of spraying is substrate, path adopts Z-shaped round about manner, spray and be set as 5-15 minute interval time, shower nozzle translational speed is 0.5-2mm/s, and needle tubing flow is 0.5-2mL/min; The vertical range of shower nozzle and substrate superior pole piece is 15-30cm.
9. the method for claim 1, is characterized in that: described substrate dried in place temperature is 50-70 ℃.
10. for the preparation of a dried in place spraying equipment for lithium ion battery polymer gel electrolyte barrier film, it is characterized in that: it comprise place the spraying substrate of pole piece, for heating heating plate, shower nozzle and the removable mechanical arm of substrate; Described heating plate one end is provided with the concavo-convex draw-in groove chimeric with removable mechanical arm one end, and shower nozzle is placed in the removable mechanical arm other end; On the suprabasil pole piece of described shower nozzle spraying mixt under it; Described substrate is placed on heating plate.
CN201310556913.7A 2013-11-11 2013-11-11 Method for preparing lithium ion battery polymer gel electrolyte membrane Pending CN103560220A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548636A (en) * 2019-09-05 2019-12-10 大连理工大学 Automatic spraying device for preparing film material
US20220115693A1 (en) * 2020-10-08 2022-04-14 Ut-Battelle, Llc Method of manufacturing a thin film composite solid electrolyte

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1468452A (en) * 2000-08-11 2004-01-14 ƽ Lithium battery with retained gel-electrolyte
US20110003210A1 (en) * 2009-07-03 2011-01-06 Korea Institute Of Industrial Technology Polyolefin Microporous Membrane Surface-Modified By Hydrophilic Polymer, Surface Modification Method Thereof And Lithium-Ion Polymer Battery Including The Same
CN202377129U (en) * 2011-12-31 2012-08-15 暨南大学 Film coating machine
CN202516731U (en) * 2012-04-13 2012-11-07 中国东方电气集团有限公司 Coating machine for manufacturing membrane electrode of fuel cell

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1468452A (en) * 2000-08-11 2004-01-14 ƽ Lithium battery with retained gel-electrolyte
US20110003210A1 (en) * 2009-07-03 2011-01-06 Korea Institute Of Industrial Technology Polyolefin Microporous Membrane Surface-Modified By Hydrophilic Polymer, Surface Modification Method Thereof And Lithium-Ion Polymer Battery Including The Same
CN202377129U (en) * 2011-12-31 2012-08-15 暨南大学 Film coating machine
CN202516731U (en) * 2012-04-13 2012-11-07 中国东方电气集团有限公司 Coating machine for manufacturing membrane electrode of fuel cell

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548636A (en) * 2019-09-05 2019-12-10 大连理工大学 Automatic spraying device for preparing film material
US20220115693A1 (en) * 2020-10-08 2022-04-14 Ut-Battelle, Llc Method of manufacturing a thin film composite solid electrolyte

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Application publication date: 20140205