CN101154750A - High power gel polymer lithium ion power cell and method of producing the same - Google Patents
High power gel polymer lithium ion power cell and method of producing the same Download PDFInfo
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- CN101154750A CN101154750A CNA2006100537638A CN200610053763A CN101154750A CN 101154750 A CN101154750 A CN 101154750A CN A2006100537638 A CNA2006100537638 A CN A2006100537638A CN 200610053763 A CN200610053763 A CN 200610053763A CN 101154750 A CN101154750 A CN 101154750A
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- Y02E60/10—Energy storage using batteries
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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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Abstract
The invention relates to a lithium ion battery and the manufacturing method thereof, particularly relating to a high multiplying power gel polymer lithium ion power battery and the manufacturing method thereof. Mainly aiming at resolving the technical problems of safety performance, etc., which exists in the prior art, the invention provides the high multiplying power gel polymer lithium ion power battery, which has the advantages of reasonable design, simple structure, high safety performance and low cost, and the manufacturing method thereof. The main technical proposal of the invention is that the lithium ion power battery consists of a cathode mass flow liquid, an anode mass flow liquid, a cathode membrane, an anode membrane, a membrane and electrolyte, wherein, the membrane is the gel polymer electrolyte, the cathode membrane and the anode membrane are evenly coated or hot-pressed on the cathode mass flow liquid and the anode mass flow liquid; the cathode mass flow liquid, the cathode membrane, the membrane, the anode membrane and the anode mass flow liquid are orderly overlaid, forming a square single bag.
Description
Technical field
The invention belongs to the lithium ion battery and the manufacture method thereof of electrochemical field, especially relate to a kind of high power gel polymer lithium ion power cell and manufacture method thereof.
Background technology
The whole world face day by day serious environmental problem and following oil equal energy source will exhausted situation under, seeking regenerative resource has become human urgent task.One of novel green power supply that electrokinetic cell is given priority to as present world developed country has better market prospect at aspects such as electric motor car, electric tool, mobile electronic devices.Present electrokinetic cell mainly contains three kinds of lead-acid battery, nickel-cadmium cell and lithium ion batteries, the history in existing more than 200 year of the use of lead-acid battery, but along with people's environmental consciousness constantly strengthens, it is banned use of by more and more countries, its specific energy is low also to have limited its use, and lead-acid battery more and more can not satisfy people's requirement.Nickel-cadmium cell is because memory effect and cadmium pollution, its output also will reduce gradually, and that lithium ion battery has is pollution-free, memory-less effect, specific energy height (energy density be lead-acid battery 3-4 doubly, 2 times of Ni-MH battery), advantage such as light weight, obtained fast development in recent years, in mobile communication and notebook computer, be widely used, aspect electrokinetic cell, also will have wide development space.
Electrokinetic cell requires higher relatively to aspects such as security performance, specific powers, polymer Li-ion battery is owing to adopt the gel polymer electrolyte replacement liquid electrolyte that has ionic conductivity and have the barrier film effect concurrently, do not have free liquid electrolyte to exist, improved the security performance of battery greatly.But the high rate capability of gel polymer lithium ion battery can't satisfy the needs of electric motor car, awaits further to improve.
Polymer lithium ion power cell on the market is liquid and flexible package type lithium ion battery at present, it as a kind of domestic patent No. 02149399.5 flexible package liquid lithium ion accumulator, its content is: the shell of storage battery is the flexible package body with plastic-aluminum combined film production, in the flexible package wall is the hard fixed mount of self-contained battery utmost point group, fixed mount is the porous framework shape that metal material or nonmetallic materials are made, the also hard fixed mount of shell, internal layer flexible package packaged battery utmost point group.The research of gel-type polymer lithium-ion-power cell is very few, and patent of the present invention is primarily aimed at the gel-type polymer lithium-ion-power cell and has carried out detailed elaboration.
Summary of the invention
The present invention mainly is the technical problem that solves existing in prior technology security performance etc.; Provide a kind of reasonable in design, simple in structure, expensive cheap high power gel polymer lithium ion power cell of security performance and manufacture method thereof.
It is that solution existing in prior technology battery capacity is low that the present invention also has a purpose, and charge-discharge performance is the high-technology problem not; Provide a kind of high magnification, high power gel polymer lithium ion power cell that charge-discharge performance is good and manufacture method thereof.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals: lithium-ion-power cell is made up of anode and cathode collector, anode and cathode film, barrier film and electrolyte, barrier film is a gel polymer electrolyte, at even anode and cathode film in coating or the hot pressing on the anode and cathode collector, being superposeed successively by cathode current collector, cathodic coating, barrier film, anode film, anode collector forms square single the bag.
As preferably, described electric in-core bilge construction mainly is made of three kinds of composite components:
A. the composite component formed by cathodic coating and cathode current collector of cathode sheets,
B. the composite component formed by anode film and anode collector of anode strip,
C. barrier film is a kind of gel polymer electrolyte film.
As preferably, described cathode current collector is aluminium net or punching aluminium foil, and cathodic coating is made up of cathode active material+conductive agent+binding agent+plasticizer, and cathodic coating coating or hot pressing are on cathode current collector one side surface or two-sided surface; Described cathode active material is the combination of one or more lithium intercalation oxides, for example lithium and cobalt oxides, lithium manganese oxide, lithium nickel oxide, lithium-cobalt-nickel oxide or their solid solution etc.; Conductive agent is various high conductivity carbon blacks, and for example acetylene black, acetone are black, SupperS, Supper P and superfine graphite powder etc.; Binding agent is a polymer, for example polyvinylidene fluoride homopolymer, vinylidene fluoride-hexafluoropropylene copolymer etc.
As preferably, described anode collector is copper mesh, Copper Foil or punching Copper Foil, and anode film is made up of anode active material+conductive agent+binding agent+plasticizer, and anode film coating or hot pressing are on one side surface, anode current collector surface or two-sided surface; Described anode active material is the combination of one or more carbonaceous materials, and for example natural or synthetic graphite, carbonaceous mesophase spherules and mesocarbon fiber etc. can make lithium ion embed repeatedly and take off the graphitized carbon based material of embedding.Conductive agent is various high conductivity carbon blacks, and for example acetone is black, Supper S and Supper P etc.; Binding agent is a polymer, for example polyvinylidene fluoride homopolymer, vinylidene fluoride-hexafluoropropylene copolymer etc.
As preferably, described barrier film is a kind of apertured polymeric film, is made through organic solvent by polymeric material, inorganic filler, plasticizer.
As preferably, described polymeric material is one of Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethacrylates, polyacrylate, polyethylene, polypropylene, polypropylene, polyethylene/polypropylene trilamellar membrane, polyvinyl acetate, acrylonitrile-acrylic copolymer or combination in any; Inorganic filler is one of silicon dioxide, alundum (Al, titanium dioxide, di-iron trioxide, zirconia or combination in any; Plasticizer is one of repefral (DMP), dibutyl phthalate (DBP), ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate or combination in any; Solvent is acetone, butanone, cyclohexanone, oxolane and cyclohexane, isobutanol, N-methyl pyrrolidone, N, one of dinethylformamide, ethyl acetate or combination in any.
The component of described electrolyte is formulated by adding one or more lithium salts in the mixed solvent of two or more organic solvent.Described solvent is one of vinyl carbonate, propylene carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, diethyl carbonate, gamma-butyrolacton, sultone or combination in any, and described lithium salts is one of them or its mixture such as lithium perchlorate, lithium hexafluoro phosphate, LiBF4, fluorocarbon based fluorine oxygen lithium phosphate and fluorocarbon based sulfonic acid lithium.
Therefore, the present invention has following advantage: manufacturing cost and use cost is cheap, a kind of powerful gel polymer lithium ion electrokinetic cell is provided, adopt square stacked battery structure to make high power capacity high magnification gel type Li-ion electrokinetic cell, guaranteeing the high-octane while, its charge-discharge performance is well improved under big electric current; The present invention on the basis of liquid lithium ionic cell and flexible package polymer Li-ion battery, high power capacity, the high ratio polyalcohol lithium ion power cell of a kind of new type gel attitude of research and development.
Description of drawings
Accompanying drawing 1 is a multiplying power discharging property curve chart of the present invention;
Accompanying drawing 2 is cycle performance curve charts of the present invention;
Embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1:
The manufacturing of battery pole piece:
A. the preparation of positive electrode
65~95% positive electrode active materials, 1~10% conductive agent, 5~15% binding agents and 5~15% plasticizer are mixed and made into slurries in acetone, slurries are coated on the PET film, obtain the negative electrode diaphragm after the oven dry.
Wherein, described cathode active material is the combination of one or more lithium intercalation oxides, for example lithium and cobalt oxides, lithium manganese oxide, lithium nickel oxide, lithium-cobalt-nickel oxide or their solid solution etc.; Conductive agent is various high conductivity carbon blacks, and for example acetylene black, acetone are black, SupperS, Supper P and superfine graphite powder etc.; Binding agent is a polymer, for example polyvinylidene fluoride homopolymer, vinylidene fluoride-hexafluoropropylene copolymer etc.; Plasticizer is one of repefral (DMP), dibutyl phthalate (DBP), ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate or combination in any.
B. the preparation of negative material
65~95% negative active core-shell materials, 1~7% conductive agent, 5~20% binding agents and 5~20% plasticizer after the abundant dissolving, are coated on the PET film in acetone, obtain the anode diaphragm after the oven dry.
Wherein, described anode active material is the combination of one or more carbonaceous materials, and for example natural or synthetic graphite, carbonaceous mesophase spherules and mesocarbon fiber etc. can make lithium ion embed repeatedly and take off the graphitized carbon based material of embedding.Conductive agent is various high conductivity carbon blacks, and for example acetone is black, Supper S and Supper P etc.; Binding agent is a polymer, for example polyvinylidene fluoride homopolymer, vinylidene fluoride-hexafluoropropylene copolymer etc.; Plasticizer is one of repefral (DMP), dibutyl phthalate (DBP), ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate or combination in any.
C. the preparation of barrier film
25~40% polymeric materials, 10~20% inorganic fillers, 40~60% plasticizer fully are dissolved into the slurry of thickness in solvent, slurries are coated on PET film or the polypropylene, polyethylene/polypropylene trilamellar membrane, make barrier film after the oven dry.
Polymeric material is one of Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethacrylates, polyacrylate, polyethylene, polypropylene, polypropylene, polyethylene/polypropylene trilamellar membrane, polyvinyl acetate, acrylonitrile-acrylic copolymer or combination in any; Inorganic filler is one of silicon dioxide, alundum (Al, titanium dioxide, di-iron trioxide, zirconia or combination in any; Solvent is acetone, butanone, cyclohexanone, oxolane and cyclohexane, isobutanol, N-methyl pyrrolidone, N, one of dinethylformamide, ethyl acetate or combination in any; Plasticizer is one of repefral (DMP), dibutyl phthalate (DBP), ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate or combination in any.
The electrolyte preparation:
The component of electrolyte is formulated by adding one or more lithium salts in the mixed solvent of two or more organic solvent; Solvent is one of vinyl carbonate, propylene carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, diethyl carbonate, gamma-butyrolacton, sultone or combination in any; Lithium salts is one of them or its mixture such as lithium perchlorate, lithium hexafluoro phosphate, LiBF4, fluorocarbon based fluorine oxygen lithium phosphate and fluorocarbon based sulfonic acid lithium.
During use: being assembled into of battery, in cathode current collector, cathode current collector is aluminium net or punching aluminium foil, makes cathode sheets with the hot pressing of cathodic coating single or double; In anode collector, anode collector is copper mesh, Copper Foil or punching Copper Foil with the hot pressing of anode film single or double; Cathode sheets, barrier film, compound the combining together of anode strip heat with making form monolithic electricity core; Determine the quantity of monolithic electricity core stack according to the design capacity size of battery; Electrolyte is annotated in dry back in vacuum drying oven after extracting, encapsulation.
As shown in Figure 1, the heavy-current discharge performance excellence, its discharge capacity under 1C multiplying power discharging electric current is 100% of a 0.3C multiplying power, and the 5C discharge capacity is the 90-100% of 0.3C discharge capacity, and the 10C discharge capacity is the 80-100% of 0.3C discharge capacity.
As shown in Figure 2, the cycle performance excellence, 1C charging 3C discharge normal temperature 500 circle circulation back capability retentions are more than 70%.
The invention belongs to electrochemical field, so the positive pole of wherein narrating is negative electrode, negative pole is anode.
Specific embodiment described herein only is that the present invention's spirit is illustrated.The technical staff of the technical field of the invention can make various modifications or replenishes or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although this paper has used terms such as anode and cathode collector, anode and cathode film, barrier film, electrolyte morely, do not get rid of the possibility of using other term.Using these terms only is in order to describe and explain essence of the present invention more easily; They are construed to any additional restriction all is contrary with spirit of the present invention.
Claims (7)
1. a high power gel polymer lithium ion power cell comprises positive plate, negative plate, barrier film and electrolyte, it is characterized in that: electric core is to be superposeed successively by cathode current collector, cathodic coating, barrier film, anode film, anode collector to form square single bag.
2. high power gel polymer lithium ion power cell according to claim 1 is characterized in that:
Electricity in-core bilge construction mainly is made of three kinds of composite components:
A. the composite component formed by cathodic coating and cathode current collector of cathode sheets.
B. the composite component formed by anode film and anode collector of anode strip.
C. barrier film is a kind of gel polymer electrolyte film.
3. high power gel polymer lithium ion power cell according to claim 2, it is characterized in that, described cathode current collector is aluminium net or punching aluminium foil or aluminium foil, cathodic coating is made up of cathode active material+conductive agent+binding agent+plasticizer, and cathodic coating coating or hot pressing are on cathode current collector one side surface or two-sided surface; Cathode active material is the combination of one or more lithium intercalation oxides; Conductive agent is various high conductivity carbon blacks.
4. high power gel polymer lithium ion power cell according to claim 2, it is characterized in that, described anode collector is copper mesh or punching Copper Foil or Copper Foil, anode film is made up of anode active material+conductive agent+binding agent+plasticizer, and anode film coating or hot pressing are on anode collector one side surface or two-sided surface; Anode active material is the combination of one or more carbonaceous materials; Conductive agent is various high conductivity carbon blacks.
5. high power gel polymer lithium ion power cell according to claim 2 is characterized in that, described barrier film is a kind of apertured polymeric film, is made through organic solvent by polymeric material, inorganic filler, plasticizer.
6. high power gel polymer lithium ion power cell according to claim 5, it is characterized in that described polymeric material is one of Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile, polymethacrylates, polyacrylate, polyethylene, polypropylene, polypropylene, polyethylene/polypropylene trilamellar membrane, polyvinyl acetate, acrylonitrile-acrylic copolymer or combination in any.Inorganic filler is one of silicon dioxide, alundum (Al, titanium dioxide, di-iron trioxide, zirconia or combination in any; Plasticizer is one of repefral (DMP), dibutyl phthalate (DBP), ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate or combination in any; Solvent is acetone, butanone, cyclohexanone, oxolane and cyclohexane, isobutanol, N-methyl pyrrolidone, N, one of dinethylformamide, ethyl acetate or combination in any.
7. the composition of the electrolyte of a high power gel polymer lithium ion power cell, it is characterized by, the component of electrolyte is formulated by adding one or more lithium salts in the mixed solvent of two or more organic solvent, solvent is one of vinyl carbonate, propylene carbonate, dimethyl carbonate, ethyl-methyl carbonic ester, diethyl carbonate, gamma-butyrolacton, sultone or combination in any, and lithium salts is one of them or its mixture such as lithium perchlorate, lithium hexafluoro phosphate, LiBF4, fluorocarbon based fluorine oxygen lithium phosphate and fluorocarbon based sulfonic acid lithium.
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