CN101515656B - Gel state polymer lithium ion battery - Google Patents
Gel state polymer lithium ion battery Download PDFInfo
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- CN101515656B CN101515656B CN200910025684XA CN200910025684A CN101515656B CN 101515656 B CN101515656 B CN 101515656B CN 200910025684X A CN200910025684X A CN 200910025684XA CN 200910025684 A CN200910025684 A CN 200910025684A CN 101515656 B CN101515656 B CN 101515656B
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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 discloses a gel state polymer lithium ion battery. Battery anode slurry active material is made by mixing lithium vanadium phosphate particles with two or more than two particle sizes or shapes. A method for mixing anode and cathode slurry is as follows: preliminary mixing is carried out for 1 to 3 hours by double planetary mixing; and the then anode and cathode slurry is sprayed to an ultrasonic mixer by a high-pressure double-roll axial extrusion device to carry out ultrasonic vibration mixing 0.5 to 2 hours. An anode sheet and a cathode sheet are coated and dried and then are made into a lithium battery semifinished product. After a gel electrolyte precursor is added, the lithium battery semifinished product is precharged and then is carried out the electrolyte thermal polymerization by a three-section heating polymerization. The gel state polymer lithium ion battery can improves the intensity of the pole piece surface of lithium vanadium phosphate material by 20 percent to more than 60mg/cm<2>. The gel state polymer lithium ion battery eliminates the air bubble occurring during the traditional slurry mixing process, shortens the time for mixing the slurry and reduces the energy consumption during the mixing process.
Description
Technical field
The invention belongs to technical field of chemical power, be specifically related to a kind of gel polymer lithium ion battery.
Background technology
Though the polymer Li-ion battery technology has realized commercialization production in enormous quantities, and sales volume is in quick growth, but its market share still is lower than 10%, be difficult to compare with the market share of liquid lithium ionic cell 90%, this may cause owing to the polymer Li-ion battery manufacturing cost generally is higher than liquid lithium ionic cell.But, but polymer Li-ion battery has thin typeization, shape is changed arbitrarily, does not have safety problems such as leakage, has very strong development potentiality, is described as lithium ion battery of future generation.
Polymer Li-ion battery has the multiple technologies type, though present oneself the first tool production scale of gel polymer lithium ion battery wherein, but still exist the subject matter of three aspects:
One, aspect battery performance, the conductivity of gel electrolyte is compared still on the low side with liquid electrolyte, relatively poor as fast charging and discharging performance and cryogenic property.
Two, in the preparation method of gel electrolyte, no matter solution-cast becomes embrane method or U.S. Bellcore method, its common problem all is that manufacturing process is loaded down with trivial details, manufacturing cost is high.Relate to a kind of preparation method and application thereof of gel state lithium ion battery polymer electrolyte as Chinese patent 200610123986.7, adopt into the film preparation polymer dielectric exactly, large-scale production is difficulty comparatively.
Three, the mode cost of polymerized in-situ is low, easily large-scale production, but monomer polymerization is incomplete, easily produces bubble in the polymerization process, can greatly destroy the interface stability of the homogeneity of gel electrolyte and gel electrolyte and electrode slice, barrier film etc.Relate to a kind of preparation method and application thereof of gel state lithium ion battery polymer electrolyte as Chinese patent 200410077528.5, adopt 60 ℃～100 ℃, one-step polymerization 30～120min, battery easily produce bubble, and bulging takes place, and influence battery performance.
Summary of the invention
Purpose of the present invention is exactly the shortcoming that overcomes existing method and gel polymer lithium ion battery, cast aside polymer film forming in the prior art, pore creating material comes together and and time-consuming, complicated process routes such as electrolyte suction, a kind of gel polymer lithium ion battery is provided, makes that technological process simplification, equipment needed thereby minimizing, activity time shorten, product cost reduces; Simultaneously, every performance of polymer Li-ion battery also is improved.
Purpose of the present invention can reach by following measure:
A kind of gel polymer lithium ion battery is made up of positive plate, negative plate and gel electrolyte, and this gel polymer lithium ion battery is made by following method:
A) the anode sizing agent active material adopts the phosphoric acid vanadium lithium particle of two or more particle diameter or shape to mix;
The phosphoric acid vanadium lithium particle of multiple particle diameter or shape is mixed the surface density that can effectively improve positive plate, and the combination of multiple phosphoric acid vanadium lithium particle can be the combination of multiple particle diameter, as the combination of big small particle diameter; The perhaps combination of multiple shape is as the combination of sphere or sheet; It also can be the combination of multiple particle diameter and shape.Wherein, the phosphoric acid vanadium lithium particle grain size is generally 0.04～15 μ m.
Consisting of of anode sizing agent: phosphoric acid vanadium lithium 70～95wt%, conductive agent 1～10wt%, binding agent 1～10wt%, thickener 0.5～10wt% (wherein each component sum satisfies 100%); Wherein conductive agent is generally selected acetylene black and/or electrically conductive graphite; Binding agent is generally selected rubber polymer, as butadiene-styrene rubber; Thickener is generally selected cellulose substances, as sodium carboxymethylcellulose.
Consisting of of cathode size: modified graphite 70～95wt%, conductive agent 1～5wt%, binding agent 1～10wt%, thickener 0.5～5wt% (wherein each component sum satisfies 100%); Except that binding agent, the same anode sizing agent of concrete material of each component.Anode and cathode slurry also need add pulpings such as entry, NMP before mixing.
B) method for mixing of anode and cathode slurry adopts the stirring of duplicate rows star to carry out 1～3 hour preliminary mixing, is ejected into through the axial extrusion device of high pressure roller then and carries out 0.5～2 hour sonic oscillation batch mixing in the ultrasonic blender;
C) with the coating of positive and negative electrode pole piece, drying, rolling, cut, make electric core, with aluminum plastic film encapsulation, make the lithium battery semi-finished product.
The positive and negative electrode pole piece can adopt the method for superpower hot air circulation to carry out drying, and the baking temperature of positive and negative electrode pole piece can be controlled at 100～130 ℃ and 90～120 ℃ (its temperature is far above the static drying process of existing multistep) respectively.Divide the positive and negative electrode utmost point cut burn-on lug and load onto barrier film after promptly can be made into electric core.The electricity core is packed into and is vacuumized behind the aluminum plastic film and hot-press sealed, reserves liquid injection port and promptly makes the lithium battery semi-finished product.
D) in the lithium battery semi-finished product, inject the gel electrolyte presoma, adopt 0.01C～0.05C current charges 1～5h that battery is changed in advance, shelve 1～3h then;
The composition of gel electrolyte presoma is mainly: electrolyte (generally consists of ethylene carbonate EC: dimethyl carbonate DMC+1M LiPF
6) 60～90wt%, methyl methacrylate MMA 5～35wt%, polyvinylidene fluoride PVDF 3～15wt%, initator 0.01～2% (wherein each of each component satisfies 100%).The crosslinking agent that also can add 1～5wt% in this presoma.
E) change in advance after, adopt that three sections hot polymerizations are legal to carry out the electrolyte thermal polymerization.
That is that all right at present is ripe for thermal-initiated polymerization technology, remains the problem that influence battery performance in inflatable, heat drum etc. in the technical process, and three sections thermal-initiated polymerization technologies that the present invention adopts have solved battery inflatable, heat well and problem such as rouse.Three sections heated polymerizable methods be specially into:
Just section is 70～100 ℃, initiated polymerization 10～20min;
50～65 ℃ in stage casing, insulation 30～40min;
70～90 ℃ of latter ends, polymerization 10～20min.
Promptly make gel polymer lithium ion battery after the electrolyte thermal polymerization, can use through changing into step again.
Compare with existing method, the present invention mainly contains following characteristics:
1, positive active material adopts being used in combination of different size and shape phosphoric acid vanadium lithium particle
The phosphoric acid vanadium lithium material granule is thin, tap density is lower, causes the surface density of pole piece to be difficult to improve, and the specific energy of battery also is difficult to increase.By being used in combination of different size and shape phosphoric acid vanadium lithium particle, solved the little problem of phosphoric acid vanadium lithium material pole piece surface density preferably, the pole piece surface density can improve 20%, reaches 60mg/cm
2More than.
2, anode and cathode slurry adopts duplicate rows star slurry mixing continuous ultrasound technology of preparing
It is comparatively extensive that duplicate rows star mixing technology is used, but have mixing time long (needs tens hours), and the bubble that produces in batch mixing is difficult to break, is trapped in and occur pin hole when causing being coated with in the slurry, even larger area slurry blank.And duplicate rows star slurry mixing continuous ultrasound technology of preparing stirs active material earlier and carries out 1～3 hour preliminary mixing by the duplicate rows star, is ejected into through the axial extrusion device of high pressure roller then and carries out 0.5～2 hour sonic oscillation batch mixing in the ultrasonic blender.
The main feature of this technology is: a, can eliminate the bubble that occurs in the traditional slurry mixed process substantially; B, shorten the time (generally amounting to 2.5～3 hours get final product) that slurry mixes greatly, reduction compounding process energy consumption reaches more than 60%.
3, coating process
The superpower heat-wind circulate drying technology of dry employing has substituted conventional segmented and has heated the shortcoming that the intrinsic efficient of static seasoning is low, the time is long.
4, gel electrolyte adopts methyl methacrylate vinegar MMA and polyvinylidene fluoride PVDF blend, adopts pre-chemical synthesis technology
MMA and PVDF blend mainly are in order to improve the mechanical performance of PMMA base polymer electrolyte system.Consisting of of gel electrolyte presoma: electrolyte (generally consists of EC:DMC+1M LiPF
6) 60～90wt%, methyl methacrylate MMA 5～35wt%, polyvinylidene fluoride PVDF 3～15wt%, crosslinking agent 1～5%, initator 0.01～2%.
In order to improve embedding lithium capacity, adopt 0.01C～0.05C current charges 1～5h that battery is changed in advance, shelve 1～3h then.
5, after the semi-finished product lithium battery changed in advance, three sections heated polymerizables of segmentation were also eliminated residual initiators
The gel generative process is exothermic reaction, can produce bubble in the gel when temperature is higher, will destroy the interface stability of the homogeneity of gel electrolyte and gel electrolyte and electrode slice, barrier film etc.Therefore, the present invention takes two sections thermal polymerization process that Gel Precursor is carried out thermal polymerization, to eliminate bubble and residual initiators.
Just section is 70～100 ℃, initiated polymerization 10～20min;
50～65 ℃ in stage casing, insulation 30～40min;
70～90 ℃ of latter ends, polymerization 10～20min.
Why the latter end elevated temperature is that gel speed is very slow because in polymerization reaction late stage, has small amount of liquid and initator is residual.Latter end is increased to temperature 70-90 ℃ again, can make that residual monomer and initator thoroughly consumes in oneself the electrolyte through being cured, can reduce the generation of side reaction in the electrolyte in the charge and discharge process, guarantees battery stability in use.
Embodiment
Embodiment 1: the gel polymer battery with 5Ah is an example
1, slurry mixes:
Select spherical phosphoric acid vanadium lithium D
50The material that is respectively 3 μ m and 7 μ m is as positive active material, and each composition proportion (wt%) of slurry is: phosphoric acid vanadium lithium 90%, acetylene black 2.5%, electrically conductive graphite 3%, butadiene-styrene rubber 3.5%, sodium carboxymethylcellulose 1%.An amount of NMP.Each composition proportion (wt%) of cathode size is: modified graphite 88.5%, electrically conductive graphite 4%, butadiene-styrene rubber 6%, sodium carboxymethylcellulose 1.5%.An amount of water.
Batch mixing is to adopt duplicate rows star slurry mixing continuous ultrasound technology of preparing, active material is stirred by the duplicate rows star tentatively mix 2h earlier, axially extrudes to be ejected into through high pressure roller then and carries out sonic oscillation batch mixing 1h in the ultrasonic blender.
2, coating: with the anode sizing agent dual coating on the thick aluminium foil of 20 μ m, with the cathode size dual coating on the thick Copper Foil of 9 μ m.
3, drying: adopt superpower heat-wind circulate drying technology, both positive and negative polarity pole piece baking temperature is controlled at 120 ℃ and 110 ℃ respectively.
4, rolling and cutting: above-mentioned pole piece after rolling, is cut into the positive/negative plate of certain size.
5, electric core is made: with the positive/negative plate that the cuts lug of burn-oning, adopt the thick membrane coil coiled electricity core of 20um.
6, encapsulation: electric core is packed in the aluminum plastic film, vacuumize, hot-press sealed is reserved liquid injection port.
7, fluid injection: inject 6g gel electrolyte presoma.The composition of presoma (wt%) is: electrolyte (1: 1 EC:DMC+1M LiPF
6) 80%, MMA 13.5%, PVDF 5%, azo two isobutyl fat AIBN 1.5%. seal.
8, change in advance: adopt 0.02C charging 1.5h that battery is changed in advance, shelve 2h then;
9, electrolyte thermal polymerization: above-mentioned battery is placed on segmentation heating in the baking oven.Just section is 70 ℃, initiated polymerization 30min; 60 ℃ in stage casing, 80 ℃ of insulation 30min. latter ends, polymerization 20min.
10, change into:
(1) constant current 0.2C charges to 3.65V;
(2) constant voltage 3.65V is that 0.05C ends to electric current;
(3) leave standstill 15min;
(4) constant current 0.2C discharges into 2V and ends;
(5) leave standstill 15min;
(6) constant current charge 0.5C charges to 4.0V;
(7) constant voltage 4.0V is that 0.05C ends to electric current;
(8) leave standstill 15min;
(9) constant current 0.5C discharges into 2.5V and ends;
(10) leave standstill 15min;
(11) constant current 0.2C charges to 3.65V;
(12) constant voltage 3.65V is that 0.05C ends to electric current;
(13) leaving standstill 15mmn finishes.
The electricity core performance
Embodiment 2: the gel polymer battery with 8.0Ah is an example
1, slurry mixes:
Select sheet phosphoric acid vanadium lithium D
50Be respectively 400nm, the material of 3 μ m and 7 μ m is a positive active material, and ratio is 1: 2: 1.Each composition proportion (wt%) of anode sizing agent is: phosphoric acid vanadium lithium 91%, acetylene black 1.5%, electrically conductive graphite 3.5%, butadiene-styrene rubber 3%, sodium carboxymethylcellulose 1%.An amount of NMP.Each composition proportion (wt%) of cathode size is: modified graphite 90%, electrically conductive graphite 4%, butadiene-styrene rubber 4.5%, sodium carboxymethylcellulose 1.5%.An amount of water.
Batch mixing is to adopt duplicate rows star slurry mixing continuous ultrasound technology of preparing, active material is stirred by the duplicate rows star tentatively mix 3h earlier, axially extrudes to be ejected into through high pressure roller then and carries out sonic oscillation batch mixing 1h in the ultrasonic blender.
2, coating: with the anode sizing agent dual coating on the thick aluminium foil of 20 μ m, with the cathode size dual coating on the thick Copper Foil of 12 μ m.
3, drying: adopt superpower heat-wind circulate drying technology, both positive and negative polarity pole piece baking temperature is controlled at 115 ℃ and 100 ℃ respectively.
4, rolling and cutting: above-mentioned pole piece after rolling, is cut into the positive/negative plate of certain size.
5, electric core is made: with the positive/negative plate that the cuts lug of burn-oning, adopt the thick membrane coil coiled electricity core of 20um.
6, encapsulation: electric core is packed in the aluminum plastic film, vacuumize, hot-press sealed is reserved liquid injection port.
7, fluid injection: inject 10g gel electrolyte presoma.The composition of presoma (wt%) is: electrolyte (1: 1 EC:DMC+1M LiPF
6) 77%, MMA10%, PVDF 8.5%, crosslinking agent TEGDMA (the two third methyl olefin(e) acid esters of triethylene glycol) 3%, azo two isobutyl fat AIBN 1.5% seal.
8, change in advance: adopt 0.015C charging 2h that battery is changed in advance, shelve 2.5h then;
9, electrolyte thermal polymerization: battery is placed on segmentation heating in the baking oven.Just section is 75 ℃, initiated polymerization 20min; 55 ℃ in stage casing, insulation 35min; 85 ℃ of latter ends, polymerization 10-20min.
10, change into:
(1) constant current 0.2C charges to 3.65V;
(2) constant voltage 3.65V is that 0.05C ends to electric current;
(3) leave standstill 15min;
(4) constant current 0.2C discharges into 2V and ends;
(5) leave standstill 15min;
(6) constant current charge 0.5C charges to 4.0V;
(7) constant voltage 4.0V is that 0.05C ends to electric current;
(8) leave standstill 15min;
(9) constant current 0.5C discharges into 2.5V and ends;
(10) leave standstill 15min;
(11) constant current 0.2C charges to 3.65V;
(12) constant voltage 3.65V is that 0.05C ends to electric current;
(13) leaving standstill 15min finishes.
The electricity core performance
Claims (6)
1. a gel polymer lithium ion battery is made up of positive plate, negative plate and gel electrolyte, it is characterized in that this gel polymer lithium ion battery made by following method:
(A) the anode sizing agent active material adopts the phosphoric acid vanadium lithium particle of two or more particle diameters or shape to mix;
(B) method for mixing of anode and cathode slurry adopts the stirring of duplicate rows star to carry out 1～3 hour preliminary mixing, is ejected into through the axial extrusion device of high pressure roller then and carries out 0.5～2 hour sonic oscillation batch mixing in the ultrasonic blender;
(C) both positive and negative polarity pole piece coating, drying are made electric core and are packaged into the lithium battery semi-finished product, add the gel electrolyte presoma again after, battery is changed in advance;
(D) after changing in advance, adopt three sections heated polymerizable methods to carry out the electrolyte thermal polymerization;
Wherein said three sections heated polymerizable methods are:
Just section is 70～100 ℃, initiated polymerization 10～20min;
50～65 ℃ in stage casing, insulation 30～40min;
70～90 ℃ of latter ends, polymerization 10～20min.
2. gel polymer lithium ion battery according to claim 1 is characterized in that the phosphoric acid vanadium lithium particle grain size is 0.04～15 μ m.
3. gel polymer lithium ion battery according to claim 1 is characterized in that consisting of of described anode sizing agent: phosphoric acid vanadium lithium 70～95wt%, conductive agent 1～10wt%, binding agent 1～10wt%, thickener 0.5～10wt%.
4. gel polymer lithium ion battery according to claim 1, it is characterized in that consisting of of described cathode size: modified graphite 70～95wt%, conductive agent 1～5wt%, binding agent 1～10wt%, thickener 0.5～5wt%, above-mentioned each component sum is 100wt%.
5. gel polymer lithium ion battery according to claim 1, the composition that it is characterized in that described gel electrolyte presoma is mainly: electrolyte 60～90wt%, methyl methacrylate 5～35wt%, polyvinylidene fluoride 3～15wt%, initator 0.01～2%.
6. gel polymer lithium ion battery according to claim 1 is characterized in that described pre-chemical synthesis technology is: adopt 0.01C～0.05C current charges 1～5h, shelve 1～3h then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200910025684XA CN101515656B (en) | 2009-03-06 | 2009-03-06 | Gel state polymer lithium ion battery |
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|---|---|---|---|
| CN200910025684XA CN101515656B (en) | 2009-03-06 | 2009-03-06 | Gel state polymer lithium ion battery |
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| CN101515656B true CN101515656B (en) | 2011-04-27 |
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| CN103545553A (en) * | 2012-07-11 | 2014-01-29 | 兴能高科技股份有限公司 | Manufacturing method of colloid lithium battery |
| CN113903976B (en) * | 2021-09-27 | 2023-05-23 | 蜂巢能源科技有限公司 | Application method of ion-conducting gel copolymer for battery cell and battery cell |
| CN113675479B (en) * | 2021-10-21 | 2022-02-11 | 惠州市纬世新能源有限公司 | Preparation process and application of gel lithium battery |
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