CN103996877A - Method for processing lithium ion battery cell by diaphragm coating - Google Patents
Method for processing lithium ion battery cell by diaphragm coating Download PDFInfo
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- CN103996877A CN103996877A CN201310613984.6A CN201310613984A CN103996877A CN 103996877 A CN103996877 A CN 103996877A CN 201310613984 A CN201310613984 A CN 201310613984A CN 103996877 A CN103996877 A CN 103996877A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
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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
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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 the field of battery processing and discloses a method for processing a lithium ion battery cell by diaphragm coating. The method comprises the following steps of 1, diaphragm coating, 2, cell rolling, 3, liquid injection, wherein a liquid injection amount of the lithium ion battery subjected to diaphragm coating is represented by G2 and G2=G1+G1*(T2/T1)*K, 4, pre-charging, 5, hot and cold pressing and 6, formation. The method prolongs a lithium ion battery cycle life and improves lithium ion battery electrochemical performances and safety.
Description
Technical field
The present invention relates to battery manufacture field, especially relate to a kind of method that can improve the chemical property of lithium ion battery and the utilization of security performance coating barrier film processing lithium ion battery cell.
Background technology
Lithium ion battery since emerging, high with respect to energy density that other secondary cells were had with it, have extended cycle life, the advantage such as self-discharge rate is little, memory-less effect and environmental protection, become the battery of tool competitive advantage in field of chemical power source.At present, lithium ion battery has been widely used in the even field such as Aero-Space of notebook computer, digital product and electric automobile, hybrid vehicle.
Yet, along with the extensive use of lithium ion battery, frequently there is the leakage of lithium ion battery in mobile phone, notebook computer, electric bicycle, the even security incident of blast on fire.Therefore, the safety problem of lithium ion battery is paid close attention to widely, and the security performance that improves lithium ion battery is the focus of the urgent research of field of batteries always.For improving the security performance of lithium ion battery, people set about research from improving the each side such as structure, electrolysis additive, membrane surface modification of positive and negative pole material.Wherein, the basement membrane of barrier film being applied to modification is one of important directions improving lithium ion battery safety performance.
Along with the development of technology and perfect, along with the kind of separator product constantly increases, the performance of new separator product has also obtained improving significantly.But traditional lithium ion battery making technology can not meet the production requirement of novel coating barrier film, can not give full play to the good characteristic of novel coating barrier film.
Summary of the invention
For overcoming the shortcoming of traditional lithium ion battery making technology, the object of the present invention is to provide a kind ofly can meet the requirement to preparation technology in the manufacturing of lithium ion battery of novel coating barrier film, improve the method for the chemical property of lithium ion battery and the processing lithium ion battery cell of security performance.
The object of the invention is to realize by following technical measures, a kind of method that applies barrier film processing lithium ion battery cell of utilizing, comprises the following steps:
(1), apply barrier film; A surface-coated layer of gel polymer coating at basement membrane; Another surface-coated one deck ceramic coating at basement membrane;
(2), volume core; By the corresponding gel polymer coating of positive plate, the corresponding ceramic coating of negative plate, by reeling or lamination making rolling core;
(3), fluid injection; Adopt the reservoir quantity G2 of the lithium ion battery that applies barrier film to be:
G2=G1+G1*(T2/T1)*K;
Wherein, G1--traditional handicraft reservoir quantity;
G2--adopts the reservoir quantity of the lithium ion battery that applies barrier film;
The thickness of the common uncoated barrier film of T1--;
T2--applies the coating layer thickness of barrier film;
K--adjusts coefficient, and size is 20%-70%;
(4), precharge; The battery core of the staged current constant mode that adopts 0.01-0.1C after to fluid injection charged, thereby forms the relatively SEI film of even compact of one deck in negative terminal surface, and its charge volume accounts for the 20%-40% of battery capacity; Described staged current constant mode is in the different stages, and charging current is different, becomes successively large;
(5), cold-hot pressure; First by hot pressing, make gel polymer coating swelling under hot conditions, it is bonded together adding to depress with positive plate, then by the sizing of colding pressing; Hot compression parameters: temperature is 50-85 ℃, pressure is 0.2-0.6MPa, the time is 1-10min; Parameter: the 0-30 ℃ that colds pressing, pressure 0.2-0.6MPa, the time is 1-10min;
(6), change into; Adopt the charging of staged current constant mode, in the different stages, charging current is different, becomes successively large, and size of current is 0.1-0.5C, and its charge volume accounts for the 60%-100% of battery capacity.
Concrete, described in also comprise two envelopes, aging, partial volume operation after changing into.
As a kind of optimal way, the material of described basement membrane is polypropylene, polyethylene, Kynoar or polytetrafluoroethylene.
As a kind of optimal way, the thickness of described gel polymer coating is 0.5-3 μ m.
As a kind of optimal way, the thickness of described ceramic coating is 2-5 μ m.
As a kind of optimal way, the gelatin polymer coating in described step (1) is oiliness system or water-based system.
As a kind of optimal way, the coating ceramic size used in described step (1) is water-based system.
Concrete, the staged constant current charge in described step (4) is that the first stage charges: 0.05C constant current charge 120min, cut-ff voltage 3.95V; Second stage charging: 0.1C constant current charge 120min, cut-ff voltage 3.95V.
Concrete, the ladder constant current charge in described step (6) is that the first stage charges: 0.1C constant current charge 210min, cut-ff voltage 3.95V, second stage charging: 0.2C constant current charge 60min.
In order to prevent that battery core is short-circuited in cold-hot pressure process, on the battery core negative electrode lug in described step (5) after precharge, put heat-shrinkable T bush.
Content of the present invention has adopted a kind of new lithium ion battery preparation technology, compare with traditional preparation technology, in battery core manufacturing process, the reservoir quantity of battery core, chemical synthesis technology are adjusted, and in battery core formation process, increased cold-hot pressure technique, meet greatly the requirement of coat film to lithium ion battery preparation technology, can effectively improve electrical property and the security performance of lithium ion battery.Polyalkene diaphragm has hydrophobicity, and lithium ion battery electrolyte used is the polar organic solvent adopting, and barrier film is poor to the absorbability of electrolyte and wetting property.Yet the polymer coating on barrier film and ceramic coating have changed the interfacial structure of barrier film and electrolyte, the contact angle of barrier film and electrolyte is diminished, strengthened the wetting property of barrier film to electrolyte, also increased the uptake of electrolyte.If according to traditional reservoir quantity design, the amount of electrolyte can not meet lithium ion battery needs in use, has restricted the useful life of battery.Adopt new fluid injection, can conveniently calculate the best reservoir quantity of electrolyte, meeting lithium ion battery is in use demand, has extended the cycle life of lithium ion battery.Lithium ion battery is in first charge-discharge process, i.e. before lithium ion starts to embed graphite electrode (> 0.3V), organic electrolyte can form the SEI film that one deck electronic isolation, ion can be led in carbon negative terminal surface, and the performances such as the electrochemistry of the uniformity of SEI film, compactness etc. and battery, safety are closely related.On basement membrane, applied one layer of polymeric coating, in more traditional technique, not for the preparation technology that gel coat and pole piece are bonded together, improved the transporting of lithium ion between both positive and negative polarity, the electrical property of lithium ion battery and security performance are raise.The present invention reforms traditional chemical synthesis technology, the process of lithium ion battery activation is divided into precharge and changes into two parts, and increased cold-hot pressure technique in precharge with in the middle of changing into, not only can guarantee that negative terminal surface forms the SEI film of one deck even compact, and the polymer-coated layer of barrier film can be bonded together closely with positive plate.Before battery changes into, after fluid injection one envelope, increase little pre-charge galvanic process, effectively guaranteed the formation condition of SEI.Because 3.0-3.5V is the main formation interval of SEI film, adopt little electric current current constant mode charging to form the relatively SEI film of even compact of one deck in negative terminal surface.After precharge, increase cold-hot pressure technique, first by hot pressing, make gel polymer coating swelling under hot conditions, under certain pressure, be bonded together with positive plate, then by the sizing of colding pressing.After gelatin polymer Electolyte-absorptive, reduced the free liquid electrolyte of inside battery.By cold-hot pressure technique, can make positive plate and gel polymer coating can be good at being bonded together, increase the hardness of battery, reduced the thickness of battery core, improved the volumetric specific energy of battery, also shortened the transmission range of lithium ion at inside battery, reduced the internal resistance of battery simultaneously.After cold-hot pressure, again battery is changed into, thoroughly excite the activity of both positive and negative polarity active material, make it change into the material with normal electrical chemical action, guarantee the chemical property of lithium ion battery.
Adopt new method of the present invention, have the advantage of following several respects:
1, can calculate fast and accurately the best reservoir quantity of novel coating barrier film, meet lithium ion battery demand in use, the cycle life that has extended lithium ion battery;
2, gel polymer coating and positive pole are bonded together preferably, have reduced resistance and the distance of lithium ion transmission, strengthened the hardness of battery, improved chemical property and the security performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is gel polymer coating and anodal bond effect figure in the embodiment of the present invention;
Fig. 2 is the multiplying power discharging curve chart of the embodiment of the present invention and comparative example;
Fig. 3 is the cycle performance of battery comparison diagram of the embodiment of the present invention and comparative example.
embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment:
Utilize a method that applies barrier film processing lithium ion battery cell, comprise the following steps:
(1), apply barrier film; A surface-coated layer of gel polymer coating at basement membrane; Another surface-coated one deck ceramic coating at basement membrane; The thickness of gel polymer coating is 0.5-3 μ m, and gelatin polymer coating is oiliness system or water-based system, and the thickness of ceramic coating is 2-5 μ m, and applying ceramic size used is water-based system;
In the present embodiment, adopting thickness is the coating barrier film of 20 μ m, and wherein basement membrane thickness is that 16 μ m, gelatin polymer coat thickness are that 1 μ m, ceramic coated layer thickness are 3 μ m; The material of basement membrane can be selected any in polypropylene, polyethylene, Kynoar or polytetrafluoroethylene.
(2), volume core; By the corresponding gel polymer coating of positive plate, the corresponding ceramic coating of negative plate, by reeling or lamination making rolling core; The volume core that is coiled into 494068P-1500mAh of take in the present embodiment describes as example;
Then will roll up core after the operations such as hot pressing shaping, insulation short-circuit test, top side seal, high-temperature vacuum baking, and take out and put into glove box preparation fluid injection;
(3), fluid injection; Adopt the reservoir quantity G2 of the lithium ion battery that applies barrier film to be:
G2=G1+G1*(T2/T1)*K;
Wherein, G1--traditional handicraft reservoir quantity;
G2--adopts the reservoir quantity of the lithium ion battery that applies barrier film;
The thickness of the common uncoated barrier film of T1--;
T2--applies the coating layer thickness of barrier film;
K--adjusts coefficient, and size is 20%-70%;
Setting and adopting conventional barrier film fluid injection coefficient is 350mAh/g, according to above-mentioned reservoir quantity formula, calculate so, the best reservoir quantity of each battery core equals 4.72g, adjustment coefficient in the present embodiment is 40%, (traditional handicraft reservoir quantity G1=1500/350g=4.29g, the G2=4.29+4.29*(4/16 of each battery core) * 40%=4.72g);
Through completing, the operation such as vacuum is standing, an envelope is taken out battery core from glove box after fluid injection, places the precharge of the laggard row order ladder of 12-24h;
(4), precharge; The battery core of the staged current constant mode that adopts 0.01-0.1C after to fluid injection charged, thereby forms the relatively SEI film of even compact of one deck in negative terminal surface, and its charge volume accounts for the 20%-40% of battery capacity; Described staged constant current charge is in the different stages, and charging current is different, becomes successively large;
Staged constant current charge is in the present embodiment, first stage charging: 0.05C constant current charge 120min, cut-ff voltage 3.95V; Second stage charging: 0.1C constant current charge 120min, cut-ff voltage 3.95V;
(5), cold-hot pressure; On battery core negative electrode lug after precharge, put heat-shrinkable T bush, be used for preventing that battery core is short-circuited in cold-hot pressure process, first by hot pressing, make gel polymer coating swelling under hot conditions, it is bonded together adding to depress with positive plate, then by the sizing of colding pressing; Hot compression parameters: temperature is 50-85 ℃, pressure is 0.2-0.6MPa, the time is 1-10min; Parameter: the 0-30 ℃ that colds pressing, pressure 0.2-0.6MPa, the time is 1-10min;
With reference to figure 1, be gel polymer coating in the present embodiment and anodal bond effect figure;
(6), change into; Adopt the charging of staged current constant mode, make its active material have normal electrochemical action, in the different stages, charging current is different, becomes successively large, and size of current is 0.1-0.5C, and its charge volume accounts for the 60%-100% of battery capacity;
Staged constant current charge is in the present embodiment, first stage charging: 0.1C constant current charge 210min, cut-ff voltage 3.95V, second stage charging: 0.2C constant current charge 60min.
After changing into, battery core completes the making of battery core through operations such as two envelopes, aging, partial volumes.
Comparative example:
Adopt material and the winding process identical with embodiment, make volume core, then volume core is carried out after hot pressing shaping, insulation short-circuit test, top side seal, high-temperature vacuum baking to taking-up and put into glove box and prepare fluid injection.
Setting fluid injection coefficient is 350mAh/g, so reservoir quantity=the 1500/350g=4.29g of each battery core.
Through completing, the operation such as vacuum is standing, an envelope is taken out battery core from glove box after fluid injection, places the laggard row order ladder of 12-24h electricizing activation.First stage: 0.05C constant current charge 200min, cut-ff voltage 3.95V; Second stage: 0.1C constant current charge 210min, cut-ff voltage 3.95V; Phase III: 0.2C constant current charge 60min, cut-ff voltage 3.95V.
After battery core activation, through operations such as two envelopes, aging, partial volumes, complete the making of battery core.
From two groups of battery cores, 10 of random chooses carry out internal resistance test respectively, table with test results 1,
Table 1
Its internal resistance of battery core of visible the present invention's processing is less.
From two groups of battery cores, the some battery cores of difference random choose, carry out security performance test, and every security performance is tested 3 of each random chooses in every group of battery core and tested, table with test results 2,
Table 2
Security performance test event | Comparative example | Embodiment |
130 ℃/30min thermal shock | OK | OK |
Normal temperature short circuit | OK | OK |
Acupuncture | NG | OK |
Heavy impact | NG | OK |
3C/5V overcharges | NG | OK |
Overdischarge | OK | OK |
Extruding | OK | OK |
Can the present invention the battery core of processing it is safer;
From two groups of battery cores, 3 battery cores of random choose are carried out multiplying power discharging property test, and multiplying power discharging curve is shown in Fig. 2, and the battery core discharge performance of visible the present invention's processing is better;
From two groups of battery cores, three battery cores of random choose are carried out the test of 1C cycle performance respectively, and 1C cyclic curve is shown in Fig. 3, and the battery core cycle life of visible the present invention's processing is longer.
More than to utilize the method that applies barrier film processing lithium ion battery cell to set forth to the present invention; be used for helping to understand the present invention; but embodiments of the present invention are not restricted to the described embodiments; anyly do not deviate from the change done under the principle of the invention, modification, substitute, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. utilize a method that applies barrier film processing lithium ion battery cell, it is characterized in that comprising the following steps:
(1), apply barrier film; A surface-coated layer of gel polymer coating at basement membrane; Another surface-coated one deck ceramic coating at basement membrane;
(2), volume core; By the corresponding gel polymer coating of positive plate, the corresponding ceramic coating of negative plate, by reeling or lamination making rolling core;
(3), fluid injection; Adopt the reservoir quantity G2 of the lithium ion battery that applies barrier film to be:
G2=G1+G1*(T2/T1)*K;
Wherein, G1--traditional handicraft reservoir quantity;
G2--adopts the reservoir quantity of the lithium ion battery that applies barrier film;
The thickness of the common uncoated barrier film of T1--;
T2--applies the coating layer thickness of barrier film;
K--adjusts coefficient, and size is 20%-70%;
(4), precharge; The battery core of the staged current constant mode that adopts 0.01-0.1C after to fluid injection charged, thereby forms the relatively SEI film of even compact of one deck in negative terminal surface, and its charge volume accounts for the 20%-40% of battery capacity; Described staged current constant mode is in the different stages, and charging current is different, becomes successively large;
(5), cold-hot pressure; First by hot pressing, make gel polymer coating swelling under hot conditions, it is bonded together adding to depress with positive plate, then by the sizing of colding pressing; Hot compression parameters: temperature is 50-85 ℃, pressure is 0.2-0.6MPa, the time is 1-10min; Parameter: the 0-30 ℃ that colds pressing, pressure 0.2-0.6MPa, the time is 1-10min;
(6), change into; Adopt the charging of staged current constant mode, in the different stages, charging current is different, becomes successively large, and size of current is 0.1-0.5C, and its charge volume accounts for the 60%-100% of battery capacity.
2. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: described in also comprise two envelopes, aging, partial volume operation after changing into.
3. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the material of described basement membrane is polypropylene, polyethylene, Kynoar or polytetrafluoroethylene.
4. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the thickness of described gel polymer coating is 0.5-3 μ m.
5. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the thickness of described ceramic coating is 2-5 μ m.
6. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the gelatin polymer coating in described step (1) is oiliness system or water-based system.
7. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the coating ceramic size used in described step (1) is water-based system.
8. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the staged constant current charge in described step (4) is that the first stage charges: 0.05C constant current charge 120min, cut-ff voltage 3.95V; Second stage charging: 0.1C constant current charge 120min, cut-ff voltage 3.95V.
9. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: the ladder constant current charge in described step (6) is, first stage charging: 0.1C constant current charge 210min, cut-ff voltage 3.95V, second stage charging: 0.2C constant current charge 60min.
10. utilization according to claim 1 applies the method for barrier film processing lithium ion battery cell, it is characterized in that: on the battery core negative electrode lug in described step (5) after precharge, put heat-shrinkable T bush.
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