CN101771174A - Crust polymer lithium ion battery - Google Patents
Crust polymer lithium ion battery Download PDFInfo
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- CN101771174A CN101771174A CN200810220750A CN200810220750A CN101771174A CN 101771174 A CN101771174 A CN 101771174A CN 200810220750 A CN200810220750 A CN 200810220750A CN 200810220750 A CN200810220750 A CN 200810220750A CN 101771174 A CN101771174 A CN 101771174A
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- ion battery
- lithium ion
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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
- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to a lithium ion secondary battery, in particular to a crust polymer lithium ion battery and a manufacturing method thereof applicable to automobile batteries. The crust polymer lithium ion battery comprises an anode and a cathode, and is characterized in that: polymer films are arranged on surfaces of the anode and the cathode, and a separation film is arranged between the anode and the cathode. The manufacturing method of the polymer lithium ion battery comprises steps of pole piece preparation, polymer coating, nude cell assembling, cell soaking and the like. Polymer gel electrolyte is creatively used in the lithium ion battery to improve performances of the battery, so as to achieve the purpose of meeting the performance requirements of the automobile battery, and the gel polymer electrolyte is formed by swelling the polymer films on the surfaces of the electrodes through an electrolyte solvent. Volumes of the polymer films on the surfaces of the electrodes are increased when in swelling due to crust packaging, and a good interface is formed between the electrodes and the separation films.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery, especially refer to a kind of crust polymer lithium ion battery and manufacture method thereof, be applicable to automobile batteries.
Background technology
In the existing lithium battery manufacturing technology, polymer Li-ion battery has formed good interface owing at pole piece with between isolating gel electrolyte is arranged, and can satisfy the harsh requirement of automobile batteries.
After polymerization thing lithium battery has multiple manufacture method, and wherein a kind of typical method is U.S. bell communication research institute (BELLCORE, USA) a kind of plasticizing attitude method for preparing polymer electrolytes (US Patent 5296318) of announcing in 1994.Though the operation of finishing in drying shed in the whole manufacturing process of this method is less relatively, needs extracting operation, and the automated production difficulty is big.The manufacture method that also has a kind of gel electrolyte battery is to add the prepolymer (for example copolymer of oxirane and expoxy propane) that can form gel in liquid electrolyte, carry out polymerization crosslinking in the electric core stage, thereby the polymer after crosslinked pins electrolyte solvent and electrolyte forms gel electrolyte.The defective of this method is that to contain the electrolyte viscosity of performed polymer very big, and the diffusion difficulty causes electrolyte inhomogeneous easily.It also is another major reason that this method is difficult to produce in batches that electricity core stage polymerization crosslinking degree is difficult to control.Sony has been announced the manufacture method of another kind of (CN1275816A) gel electrolyte lithium ion battery in China in the time of 2000.This method is to apply gel electrolyte on electrode, forms good gel electrolyte and barrier film interface by heating and pressurizing.The lithium salts that the shortcoming of this method is in the electrolyte to be contained having under the environment of water and can decomposing, has a strong impact on battery performance.So this method only is adapted at the following after polymerization thing lithium batteries of making of the in check environment of moisture such as drying shed.Operation has increased production cost of cells in the too much drying shed.And preparation is during gel electrolyte, because the effumability of low boiling point solvent, the gel electrolyte consistency that contains low boiling point solvent in applying the operation process is extremely rambunctious.If select for use high boiling solvent to prepare gel electrolyte, not only can cause the coating Working Procedure Controlling difficulty of gel electrolyte, also can cause the poor performance at low temperatures of electric core.Also have human vinylidene and hexafluoropropylene (PVDF-HEP) to make the gel lithium ion battery, but the cost of manufacture height, cause the lithium ion battery cost performance of being produced low, the market competitiveness is little.
Summary of the invention
One of purpose of the present invention provides the polymer Li-ion battery that a kind of technology is simple, cost of manufacture is low.
To achieve these goals, the present invention adopts following technical scheme:
Crust polymer lithium ion battery of the present invention comprises positive pole and negative pole, it is characterized in that: described positive pole and negative terminal surface are provided with polymer film, are provided with barrier film between described positive pole and the negative pole, are provided with gel electrolyte between positive pole and negative pole and the barrier film.
Preferably, negative pole is to be matrix with the collector, and material with carbon element maybe can carry out material that lithium embedded/took off embedding and be coated on the collector after as mixing such as active material, bonding agent and conductive agents and form.
Preferably, anodal is basic raw material by the oxide that contains lithium and can be used as the transition metal of secondary lithium-ion cathode active material, and chemical formula is:
Li
zM
xN
aC
bO
yWherein M is a transition metal, for example cobalt (Co), manganese (Mn), nickel (Ni) or other transition region metallic element.N and C are metallic element, as nickel (Ni), manganese (Mn), aluminium (Al) and magnesium elements such as (Mg).X, y and z are natural number, and a and b are nonnegative integer.
Preferably, the barrier film of described separation both positive and negative polarity is that polyolefin is the microporous membrane of Base Material.
Preferably, described both positive and negative polarity and barrier film are formed naked electric core, and described naked electric core is winding-structure or lamination.
Preferably, described naked electric core is installed pack case outward, and described pack case is aluminium matter duricrust or stainless steel case.
The present invention also provides a kind of manufacture method of polymer Li-ion battery, it is characterized in that: comprise the steps:
101, pole piece preparation;
102, coated polymer;
103, be assembled into naked electric core;
104, soak electric core;
105, plasticizing;
106, except that desolvating;
107, be packaged into electric core
109, inject electrolyte, sealing;
109, change into.
Preferably, in the naked electric core step of described assembling, to reel or the mode of lamination is assembled into naked electric core.
Preferably, the described solvent step of removing is removed and is desolvated for naked electric core is carried out vacuum bakeout.
The objective of the invention is to overcome above shortcoming, and in lithium ion battery, improve the performance of battery in a creative way with gel-form solid polymer electrolyte, reach the purpose that satisfies the automobile batteries performance requirement.To contain the cellulose acetate-butyrate ester of lithium electrolyte cheaply and not, or the different cellulose acetate-butyrate ester admixture of hydroxy radical content, or be prepared into polymer solution with its polymer-modified being dissolved in certain solvent that serves as other group is added on the basis, be coated to electrode surface and make film.Then with electrode and barrier film to reel or the mode of lamination is combined into naked electric core, and soak with an amount of solvent (ethylene carbonate etc.), take out electric core heating and pressurizing plasticizing to promote forming uniform interface between electrode and barrier film, carry out vacuum bakeout again, remove the plasticizing solvent.After having toasted, the electricity core goes into aluminum hull or stainless steel case.Inject electrolyte and also wear out under suitable temperature, the polymer film by solvent swell electrode surface in the electrolyte forms gel polymer electrolyte.Owing to be the duricrust packing, electrode surface polymer film volume when swelling increases, and can form good interface between electrode and barrier film.
Description of drawings
Fig. 1 is the structural representation behind the electrode surface coated polymer of first embodiment of the invention.
Fig. 2 is the both positive and negative polarity and the barrier film structural representation of first embodiment of the invention.
Fig. 3 is the naked core strueture schematic diagram of first embodiment of the invention.
Fig. 4 is the core strueture schematic diagram of first embodiment of the invention.
Fig. 5 is the manufacture method flow chart of second embodiment of the invention.
The object of the invention, function and advantage will be in conjunction with the embodiments, are described further with reference to accompanying drawing.
Embodiment
As depicted in figs. 1 and 2, the crust polymer lithium ion battery of present embodiment comprises positive pole 1 and negative pole 2, described anodal 1 and negative pole 2 surfaces be provided with polymer film 13, described anodal 1 and negative pole 2 between be provided with barrier film 3, be provided with gel electrolyte 4 between positive pole and negative pole and the barrier film.Be example explanation electrode structure with anodal 1 among Fig. 1, negative pole 2 structures are with anodal 1 structure, and anodal 1 is matrix with collector 11, and coating active material 12 is provided with polymer film 13 on the surface of active material.
Wherein, negative pole 2 is to be matrix with the collector, and material with carbon element maybe can carry out material that lithium embedded/took off embedding and be coated on the collector after as mixing such as active material, bonding agent and conductive agents and form.
Anodal 1 is basic raw material by the oxide that contains lithium and can be used as the transition metal of secondary lithium-ion cathode active material, and chemical formula is: Li
zM
xN
aC
bO
yWherein M is a transition metal, for example cobalt (Co), manganese (Mn), nickel (Ni) or other transition region metallic element.N and C are metallic element, as nickel (Ni), manganese (Mn), aluminium (Al) and magnesium elements such as (Mg).X, y and z are natural number, and a and b are nonnegative integer.
The barrier film 3 of described separation both positive and negative polarity is the microporous membrane of Base Material for polyolefin.
As shown in Figure 3, described anodal 1 and negative pole 2 and barrier film 3 form naked electric core, described naked electric core is winding-structure or lamination, and the structure of naked electric core is described as example with lamination among the figure.
Described naked electric core is installed pack case 5 outward, and described pack case 5 is aluminium matter duricrust or stainless steel case.
The second embodiment of the present invention provides a kind of manufacture method of polymer Li-ion battery, it is characterized in that: comprise the steps:
101, pole piece preparation;
102, coated polymer;
103, be assembled into naked electric core;
104, soak naked electric core;
105, plasticizing;
106, except that desolvating;
107, be packaged into electric core
108, inject electrolyte, sealing;
109, change into.
Wherein, electrode surface carries out polymer-coated.The method that applies can be a dipping, spraying, printing and brushing etc.
The polymer cellulose esters (CAB) that to be cellulose become through acetate and the common esterification of butyric acid, bytyry content is 17%～38%, number-average molecular weight is 10000～200000.Can be single CAB, also can be the mixture of several CAB.
The used solvent of polymer dissolution can be selected one or more from following solvent, acetone for example, ketones solvents such as methylethylketone, ethyl acetate, ester classes such as methyl acetate, heterocyclic compounds such as oxolane, carbonates such as dimethyl carbonate, and dimethyl formamide, N-methyl-pyrrolidones etc.
Barrier film and electrode can be that the mode of coiling or lamination is assembled into naked electric core.
Naked electric core is when soaked in solvent, and solvent can be from ester classes such as ethyl acetate, methyl acetates, and carbonates such as ethylene carbonate, and selecting in the dimethyl formamide, N-methyl-pyrrolidones etc. can be wherein one or more.Solvent will be lower than the solvent that requires in the right 6 to the dissolubility of the polymer of requirement in the right 4.
Naked electric core carries out the heating and pressurizing plasticizing.Naked electric core to right 9 carries out vacuum bakeout, removes the solvent that right 8 requires.
Naked electric core external packing can be used aluminium material duricrust or stainless steel case.
The electricity core adds nonaqueous electrolytic solution after the vacuum bakeout operation, sealing.
Battery changes into.
The used painting method of the present invention can be a dipping, spraying, methods such as trans-printing and brushing.The choice of Solvent scope is very wide, so long as can dissolve the polymer that will apply, and solvent that can the original bonding agent of lysis electrodes can use.Acetone for example, ketones solvents such as methylethylketone, ethyl acetate, ester classes such as methyl acetate, heterocyclic compounds such as oxolane, carbonates such as dimethyl carbonate, and dimethyl formamide, N-methyl-pyrrolidones etc., but be not limited to above solvent.Above solvent can also be selected two kinds and above formation mixed solvent for use, to improve solution property except independent use.Consider that the physical characteristic of solution selects suitable application temperature and humidity and film-forming temperature and humidity.The single face coating thickness is less than 15 microns, otherwise too thick gel layer can cause the increase of electric in-core resistance.
The cellulose esters (CAB) that coated polymer uses cellulose to be become through acetate and the common esterification of butyric acid, bytyry content is 17%～38%, number-average molecular weight is 20000～200000.Can be single CAB, also can be the mixture of several CAB, or based on its other group of interpolation polymer-modified.Can also by crosslinked reduction CAB in electrolyte dissolubility and form gel.
To be dipped in the solvent with the electric core of reeling or the lamination mode assembles, solvent can be from ethyl acetate, ester classes such as methyl acetate, carbonates such as ethylene carbonate, and dimethyl formamide, selections such as N-methyl-pyrrolidones also can be two kinds and above mixed solvents wherein.Soak the back taking-up electric core is carried out the heating and pressurizing plasticizing.Electric core after the plasticizing carries out vacuum bakeout, removes and desolvates.The selection of pressure is very important, the interface of too little insufficient pressure to form, and too big pressure can increase short risk, the pressure that the present invention recommends is that 500kPa is to 5000kPa.
The gelation operation is carried out after having annotated electrolyte and Vacuum Package.Usually the aging temperature of selecting for use is between the boiling point of temperature that forms gelation and electrolyte solvent.If temperature is low excessively, can not form gel electrolyte, and too high temperature can cause the vaporization of electrolyte solvent at all, destroy gel and barrier film and gel and interelectrode interface.The temperature that the present invention recommends is 40 to 120 ℃.
Concrete,
Anode: 93.5% graphite is active material, and 2.0% acetylene black is conductive agent, and 2.5% SBR is a bonding agent, and 2.0% sodium cellulose glycolate is a dispersant.
Negative electrode: 93.5% cobalt acid lithium, 3% acetylene black is conductive agent.3.5% poly-inclined to one side fluororesin (PVDF) is a bonding agent.
Barrier film: the polyolefin material of 40% voidage, 20 microns of thickness.
Electrolyte: EC/DMC/EMC volume ratio 4: 4: 2,1 mole of LiPF
6
Polymer is that fusing point is 230 degrees centigrade CAB-171-15, is provided by Eastman.
Temperature 60 degree, pressure 800kPa.
The major parameter and the performance of battery are as follows:
Battery size: 523448A (L * W * H=48mm * 34mm * 5.2mm)
Capacity: 1000mAh (0.2C)
Cell thickness: 5.08mm (containing aluminum hull)
Charging cut-ff voltage: 4.2V
Discharge cut-off voltage: 3.0V
The above only is the preferred embodiments of the present invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification of the present invention and accompanying drawing content to be done; or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (9)
1. a crust polymer lithium ion battery comprises positive pole and negative pole, it is characterized in that: described both positive and negative polarity surface is provided with polymer film, is provided with barrier film between the described both positive and negative polarity.
2. crust polymer lithium ion battery as claimed in claim 1, it is characterized in that: negative pole is to be matrix with the collector, and material with carbon element maybe can carry out material that lithium embedded/took off embedding and be coated on the collector after as mixing such as active material, bonding agent and conductive agents and form.
3. crust polymer lithium ion battery as claimed in claim 2 is characterized in that: anodal is basic raw material by the oxide that contains lithium and can be used as the transition metal of secondary lithium-ion cathode active material, and chemical formula is:
Li
zM
xN
aC
bO
yWherein M is a transition metal, for example cobalt (Co), manganese (Mn), nickel (Ni) or other transition region metallic element.N and C are metallic element, as nickel (Ni), manganese (Mn), aluminium (Al) and magnesium elements such as (Mg).X, y and z are natural number, and a and b are nonnegative integer.
4. crust polymer lithium ion battery as claimed in claim 3 is characterized in that: the barrier film of described separation both positive and negative polarity is that polyolefin is the microporous membrane of Base Material.
5. crust polymer lithium ion battery as claimed in claim 4 is characterized in that: described both positive and negative polarity and barrier film are formed naked electric core, and described naked electric core is winding-structure or lamination.
6. crust polymer lithium ion battery as claimed in claim 5 is characterized in that: described naked electric core is installed pack case outward, and described pack case is aluminium matter duricrust or stainless steel case.
7. the manufacture method of a polymer Li-ion battery as claimed in claim 1 is characterized in that: comprise the steps:
101, pole piece preparation;
102, coated polymer;
103, be assembled into naked electric core;
104, soak electric core;
105, plasticizing;
106, except that desolvating;
10 are packaged into electric core
109, inject electrolyte, sealing;
109, change into.
8. crust polymer lithium ion battery as claimed in claim 7 is characterized in that: in the naked electric core step of described assembling, to reel or the mode of lamination is assembled into naked electric core.
9. crust polymer lithium ion battery as claimed in claim 7 is characterized in that: the described solvent step of removing is removed and is desolvated for naked electric core is carried out vacuum bakeout.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810220750A CN101771174A (en) | 2008-12-31 | 2008-12-31 | Crust polymer lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810220750A CN101771174A (en) | 2008-12-31 | 2008-12-31 | Crust polymer lithium ion battery |
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| Publication Number | Publication Date |
|---|---|
| CN101771174A true CN101771174A (en) | 2010-07-07 |
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|---|---|---|---|
| CN200810220750A Pending CN101771174A (en) | 2008-12-31 | 2008-12-31 | Crust polymer lithium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324467A (en) * | 2011-09-13 | 2012-01-18 | 山东同大新能源有限公司 | In-situ polymerization preparation method of metal-shell colloid lithium ion battery |
| CN103560269A (en) * | 2013-11-04 | 2014-02-05 | 天津力神电池股份有限公司 | Gelled lithium ion battery |
| CN103730685A (en) * | 2013-12-17 | 2014-04-16 | 珠海汉格能源科技有限公司 | High-rate polymer lithium ion battery for electronic cigarettes |
| CN104319419A (en) * | 2014-11-10 | 2015-01-28 | 海宁兰博电源科技有限公司 | High-voltage special-shaped Li-polymer soft-package battery |
| CN112531205A (en) * | 2020-12-07 | 2021-03-19 | 湖南立方新能源科技有限责任公司 | Lithium ion battery and manufacturing method thereof |
-
2008
- 2008-12-31 CN CN200810220750A patent/CN101771174A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102324467A (en) * | 2011-09-13 | 2012-01-18 | 山东同大新能源有限公司 | In-situ polymerization preparation method of metal-shell colloid lithium ion battery |
| CN103560269A (en) * | 2013-11-04 | 2014-02-05 | 天津力神电池股份有限公司 | Gelled lithium ion battery |
| CN103730685A (en) * | 2013-12-17 | 2014-04-16 | 珠海汉格能源科技有限公司 | High-rate polymer lithium ion battery for electronic cigarettes |
| CN103730685B (en) * | 2013-12-17 | 2016-02-24 | 珠海汉格能源科技有限公司 | A kind of high-rate polymer lithium ion battery for electronic cigarette |
| CN104319419A (en) * | 2014-11-10 | 2015-01-28 | 海宁兰博电源科技有限公司 | High-voltage special-shaped Li-polymer soft-package battery |
| CN112531205A (en) * | 2020-12-07 | 2021-03-19 | 湖南立方新能源科技有限责任公司 | Lithium ion battery and manufacturing method thereof |
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Application publication date: 20100707 |