CN102147185A - Drying method of pole pieces of lithium-ion secondary battery - Google Patents
Drying method of pole pieces of lithium-ion secondary battery Download PDFInfo
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- CN102147185A CN102147185A CN2010106013740A CN201010601374A CN102147185A CN 102147185 A CN102147185 A CN 102147185A CN 2010106013740 A CN2010106013740 A CN 2010106013740A CN 201010601374 A CN201010601374 A CN 201010601374A CN 102147185 A CN102147185 A CN 102147185A
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- coiled strip
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- temperature
- pole piece
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- 238000001035 drying Methods 0.000 title claims abstract description 87
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 title abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000005096 rolling process Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000002002 slurry Substances 0.000 description 6
- 238000003475 lamination Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000029058 respiratory gaseous exchange Effects 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
Abstract
The invention provides a drying method of pole pieces of a lithium-ion secondary battery, which comprises the following steps of: respectively drying an anode coil stock and a cathode coil stock; placing the coil stocks into a pallet in a drying box; vacuumizing the drying box to -0.1MPa, then continuously vacuumizing for 1-30 minutes, and closing; heating the drying box by utilizing a heater; filling inert gas into the drying box after 2-10 hours, and stopping until the pointer of a vacuum meter reaches -0.01MPa; exchanging the inert gas with moisture in the drying box for 5-30 minutes, vacuumizing the drying box to -0.1MPa, then continuously vacuumizing for 1-30 minutes, and closing; and closing the heater, and taking the coil stocks out of the drying box to be rolled after the temperature drops to the indoor temperature. The drying method provided by the invention can be used for completely eliminating the moisture in the coil stocks of the pole pieces, thereby improving the performance of the battery and eliminating the potential safety hazards caused by the ballooning of the battery.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of drying means of lithium rechargeable battery pole piece.
Background technology
Lithium rechargeable battery has the energy height, has extended cycle life, Stability Analysis of Structures, security performance is good, cost is low, do not have any poisonous and harmful substance, not to characteristics such as any pollutions of environment structure, (for example be widely used in electronic instrument, number and household appliances at present, mobile phone, digital camera, notebook computer) on, but also applicable to the electrokinetic cell for preparing large-capacity high-power.
The manufacturing process flow of traditional lithium rechargeable battery pole piece is as follows: at first, and with solvent, binding agent, conductive agent, just/negative electrode active material etc. adds successively according to technological requirement and stirs in the agitator, obtains slurry; Then, change the slurry after making over to coating machine, and be coated on the collection liquid surface; Then, put the rolling that is coated with slurry into baking oven and carry out drying, vary in size and the characteristic difference according to surface density, the oven temperature of coating machine is arranged on 90～110 degree and does not wait; Then, to the coiled strip that obtains after the drying is rolled, technology such as section, chip select and lamination obtains the final required specification of battery complete pole piece.The coiled strip drying must be carried out before rolling, this is because the gas permeability of the coating pole piece dressing before rolling is better, heating at baking oven can be with water evaporates, and the baking of rolling back, the moisture of coating pole piece dressing inside is difficult to evaporation, this is that the space dwindles, so moisture entrapment is in coating pole piece dressing inside because after rolling the dressing of coating pole piece is compressed.
This manufacturing process flow very easily absorbs water when making pole piece, even being put into baking oven, the pole piece coiled strip carries out heat drying, can not discharge the moisture in the pole piece dressing fully, this will cause battery in charge and discharge process in the pole piece contained moisture can and the electrolyte of the battery generation gas that reacts, influence battery performance, particularly the cycle life to battery causes great influence, causes the battery bulging simultaneously easily, bring very big potential safety hazard (for example, blasting) to battery.
In order to address the above problem, in being 200810135388.0 Chinese patent application " a kind of pole piece drying equipment and drying means ", application number proposed a kind of pole piece to be dried successively to be put into the method that infrared baking vessel and air blast baking vessel toast.The resistivity of the pole piece of making by this method is little, and the material situation of falling in cyclic process reduces.But the LiFePO4 oxidation of divalent becomes ferric iron, and self discharge is big, cycle performance is poor, the gram volume performance is low.
Summary of the invention
In order to address the above problem, the invention provides a kind of drying means of lithium rechargeable battery pole piece, with the moisture in the thorough eliminating pole piece coiled strip, thereby improve battery performance and eliminate the potential safety hazard that the battery bulging is brought.
In order to realize above purpose, the drying means of lithium rechargeable battery pole piece provided by the invention separately carries out drying to anodal coiled strip and negative pole coiled strip according to following steps: step 1, coiled strip put into the pallet of drying box; Step 2, drying box is evacuated to-continue to take out behind the 0.1MPa and closed vacuum system in 1～30 minute; Step 3, utilize heater that drying box is heated; Step 4, in drying box, charge into inert gas after 2～10 hours, up to the vacuum meter pointer reach-0.01MPa stops; Step 5, allow inert gas in drying box with exchange of moisture 5～30 minutes, then drying box is evacuated to-continue to take out behind the 0.1MPa and closed in 1～30 minute; With step 6, close heater, treat that temperature is reduced to after the indoor temperature to take out coiled strip in the drying box and drop into rolling.
Preferably, it is clean that pallet keeps, and the coiled strip of putting into drying box is no more than four volumes.
Preferably, the heating-up temperature of anodal coiled strip is set to 11～130 degree in the described step 3, and the heating-up temperature of negative pole coiled strip is set to 80～90 degree.
Preferably, described inert gas is nitrogen or argon gas.
Preferably, described indoor temperature is below 30 degree.
Preferably, treat that after closing heater temperature reduces to before the indoor temperature, drying box is evacuated to-continue to take out behind the 0.1MPa and closed in 1～30 minute.
Preferably, can not treat that in step 6 temperature reduces to indoor temperature and take out coiled strip immediately in the drying box and drop under the rolling situation, the coiled strip vacuum is retained in the drying box maximum 24 hours.
Preferably, per 2～20 hours circulation repeating steps 4 and step 5, cycle-index is 5～20 times.
Preferably, the every volume length of anodal coiled strip is 250～280m, and the every volume length of negative pole coiled strip is 150～180m.
On the other hand, the invention provides a kind of pole piece manufacture method of lithium rechargeable battery, it is characterized in that, separately make anode pole piece and cathode pole piece, comprise according to any one the described drying means in the claim 1～7 and separately anodal coiled strip and negative pole coiled strip are carried out drying.
By above technical scheme, can thoroughly get rid of the moisture in the pole piece coiled strip, thereby improve battery performance (comprising that cycle life and capacity keep ratio) and eliminate the potential safety hazard that the battery bulging is brought.
Description of drawings
Fig. 1 is the flow chart according to the drying means of the lithium rechargeable battery pole piece of the first embodiment of the present invention;
Fig. 2 is the schematic flow sheet of the drying means of lithium rechargeable battery pole piece according to a second embodiment of the present invention;
Fig. 3, Fig. 4 and Fig. 5 are respectively the curve maps that the test result of scheme one, scheme two and scheme three is shown.
The specific embodiment
Below, present invention is described with embodiment with reference to the accompanying drawings.
In the present invention, consider that the mixing contact of positive and negative pole material can cause following harmful effect: (1) can cause short circuit in battery production, causes causing to later process scrapping; (2) when changing into, can cause bigger internal resistance; (3) self discharge increases; (4) potential safety hazard comprises the influence of high temperature discharge, low temperature charging; (5) influence the cycle life of battery, therefore, separately anodal coiled strip and negative pole coiled strip are carried out drying, that is to say, positive and negative electrode coiled strip separate drying is provided with different temperature according to the characteristic of product.
(first embodiment)
Fig. 1 is the flow chart according to the drying means of the lithium rechargeable battery pole piece of the first embodiment of the present invention.As described in Figure 1, this drying means may further comprise the steps:
In this step, coiled strip is put into the pallet of drying box, pallet should guarantee it is clean, and the purpose of this step is to avoid positive and negative pole material to mix contact, and cross pollution is to avoid above-mentioned harmful effect.
In this step, drying box is evacuated to-continue to take out behind the 0.1MPa and closed vacuum system in 1～30 minute.The purpose of this step is to carry out drying under the condition that makes coiled strip not have air to contact in drying box.
In this step, utilize heater that drying box is heated, wherein, heating-up temperature is arranged in the scope that every performance is not had to influence according to specification requirement, for example, heating-up temperature that can anodal coiled strip is set to 11～130 degree, and the heating-up temperature of negative pole coiled strip is set to 8090 degree.
Charge into inert gas behind step 4, the maintenance certain hour
In this step, keep in drying box, charging into inert gas after 2～10 hours, up to the vacuum meter pointer reach-0.01MPa stops, wherein, the purpose that kept 2～10 hours is to wait for carrying out next step again under the situation that moisture can evaporate, otherwise influence drying effect, the reason that charges into inert gas is not have moisture in the inert gas, for example, preferably charges into nitrogen, this is because the price comparison of nitrogen is reasonable, perhaps also can charge into argon gas.
Vacuumize behind step 5, the maintenance certain hour
In this step, allow inert gas in drying box with exchange of moisture 5～30 minutes, then drying box is evacuated to-continue to take out behind the 0.1MPa and closed in 1～30 minute.The purpose of this step is to carry out drying under the condition that makes coiled strip not have air to contact in drying box equally.
In this step, close heater, treat that temperature (for example reduces to indoor temperature, 30 degree are following) take out coiled strip in the drying box and drop into rolling, wherein, treat that it is if the too high outlet of coiled strip temperature that temperature is reduced to the reason of indoor temperature, the coiled strip and the indoor temperature temperature difference are big, moisture in the rapid absorbed air of coiled strip meeting is equivalent to not play dry purpose.If because other factors causes and can not in time be rolled, the coiled strip vacuum can be retained in the drying box maximum 24 hours, as surpassing 24 hours, then can influence the constant-current charge rate and the cycle life of battery.In addition, be further to strengthen drying effect, can treat closing heater after that temperature reduces to step that vacuumizes of increase before the indoor temperature, that is, drying box is evacuated to-continue to take out behind the 0.1MPa and closed in 1～30 minute.
In addition, can thoroughly discharge in order to guarantee the moisture in the coiled strip, preferably following control coiled strip size, that is, the every volume length of anodal coiled strip is 250～280m, the every volume length of negative pole coiled strip is 150～180m.
(second embodiment)
In order further to guarantee thoroughly to discharge the moisture in the coiled strip again, present embodiment is just closed heater after repetitive cycling ventilation on the basis of first embodiment 5 to 20 times, described ventilation comprises: keep charging into behind the certain hour inert gas (step 4) and keep vacuumizing (step 5) behind the certain hour.
Fig. 2 is the schematic flow sheet of the drying means of lithium rechargeable battery pole piece according to a second embodiment of the present invention.In Fig. 2, cyclical breathing 5 times promptly, repeats " retention time " → " inflated with nitrogen " → " retention time " → " vacuumizing " 5 times.
Below, pass test data is illustrated the battery performance contrast of dry time of different dry.
Fig. 3 is the curve map that the test result of scheme one is shown, the technological process of scheme one is: powder baking → slurry preparation → coating → rolling → section → chip select → lamination → assembling → welding → drying → fluid injection → change into → test, in scheme one, before rolling, do not carry out the coiled strip drying.As can be seen from Figure 3, when circulation 1100 times the time, it is 85.66% that battery capacity keeps ratio.
Fig. 4 is the curve map that the test result of scheme two is shown, the technological process of scheme two is: powder baking → slurry preparation → coating → drying is filled air → rolling → section → chip select → lamination → assembling → welding → drying → fluid injection → change into → test, in scheme two, before rolling, carry out the coiled strip drying, but whether charge into nitrogen but charge into room air, cyclical breathing 5～20 times.As can be seen from Figure 4, when circulation 1819 times the time, it is 83.56% that battery capacity keeps ratio.
Fig. 5 is the curve map that the test result of scheme three is shown, the technological process of scheme three is: powder baking → slurry preparation → coating → dry inflated with nitrogen → rolling → section → chip select → lamination → assembling → welding → drying → fluid injection → change into → test, in scheme three, before rolling, carry out the coiled strip drying, charge into nitrogen and take a breath, cyclical breathing 5～20 times.As can be seen from Figure 5, when circulation 1779 times the time, it is 98.96% that battery capacity keeps ratio.That is to say that at more times circulation time, it is very high that battery capacity still can keep, thereby explanation significantly improves the cycle life of battery by the inventive method, and can eliminate the potential safety hazard that the battery bulging is brought.
(the 3rd embodiment)
Present embodiment provides a kind of pole piece manufacture method of lithium rechargeable battery, the method is characterized in that, separately makes anode pole piece and cathode pole piece, that is, whole manufacturing process of anode pole piece manufacturing process flow and cathode pole piece are all separately realized.By this pole piece manufacture method, can fully discharge the moisture in the coiled strip, improve battery performance most possibly and eliminate the potential safety hazard that the battery bulging is brought to battery.
Below with reference to drawings and Examples the present invention is described in detail; but; should be appreciated that the present invention is not limited to above disclosed specific embodiment, any modification based on the disclosed technical scheme of this specification all should be included in protection scope of the present invention.
Claims (10)
1. the drying means of a lithium rechargeable battery pole piece, this method is separately carried out drying to anodal coiled strip and negative pole coiled strip according to following steps:
Step 1, coiled strip put into the pallet of drying box;
Step 2, drying box is evacuated to-continue to take out behind the 0.1MPa and closed vacuum system in 1～30 minute;
Step 3, utilize heater that drying box is heated;
Step 4, in drying box, charge into inert gas after 2～10 hours, up to the vacuum meter pointer reach-0.01MPa stops;
Step 5, allow inert gas in drying box with exchange of moisture 5～30 minutes, then drying box is evacuated to-continue to take out behind the 0.1MPa and closed vacuum system in 1～30 minute; With
Step 6, close heater, treat that temperature is reduced to after the indoor temperature to take out coiled strip in the drying box and drop into rolling.
2. drying means according to claim 1 is characterized in that, it is clean that pallet keeps, and the coiled strip of putting into drying box is no more than four volumes.
3. according to right 1 described drying means, it is characterized in that the heating-up temperature of anodal coiled strip is set to 11～130 degree in the described step 3, the heating-up temperature of negative pole coiled strip is set to 80～90 degree.
4. drying means according to claim 1 is characterized in that, described inert gas is nitrogen or argon gas.
5. drying means according to claim 1 is characterized in that, described indoor temperature is below 30 degree.
6. drying means according to claim 1 is characterized in that, treats that after closing heater temperature reduces to before the indoor temperature, drying box is evacuated to-continue to take out behind the 0.1MPa and closed in 1～30 minute.
7. drying means according to claim 1 is characterized in that, can not treat that in step 6 temperature reduces to indoor temperature and take out coiled strip immediately in the drying box and drop under the rolling situation, and the coiled strip vacuum is retained in the drying box maximum 24 hours.
8. drying means according to claim 1 is characterized in that, per 2～20 hours circulation repeating steps 4 and step 5, and cycle-index is 5～20 times.
9. drying means according to claim 1 is characterized in that, the every volume length of anodal coiled strip is 250～280m, and the every volume length of negative pole coiled strip is 150～180m.
10. the pole piece manufacture method of a lithium rechargeable battery is characterized in that, separately makes anode pole piece and cathode pole piece, comprises according to any one the described drying means in the claim 1～7 separately anodal coiled strip and negative pole coiled strip being carried out drying.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106013740A CN102147185B (en) | 2010-12-10 | 2010-12-10 | Drying method of pole pieces of lithium-ion secondary battery |
| PCT/CN2011/083047 WO2012075893A1 (en) | 2010-12-10 | 2011-11-28 | Drying method and manufacturing method of electrode sheet of lithium-ion secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010106013740A CN102147185B (en) | 2010-12-10 | 2010-12-10 | Drying method of pole pieces of lithium-ion secondary battery |
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| CN102147185A true CN102147185A (en) | 2011-08-10 |
| CN102147185B CN102147185B (en) | 2012-11-28 |
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| WO2012075893A1 (en) * | 2010-12-10 | 2012-06-14 | 奇瑞汽车股份有限公司 | Drying method and manufacturing method of electrode sheet of lithium-ion secondary battery |
| CN102901338A (en) * | 2012-10-18 | 2013-01-30 | 江苏富朗特新能源有限公司 | Drying method of pole piece for lithium ion battery |
| CN102914484A (en) * | 2012-10-16 | 2013-02-06 | 绥中正国新能源科技有限公司 | Testing method for dryness of pole piece or cell of lithium ion battery |
| CN103322776A (en) * | 2013-06-05 | 2013-09-25 | 奇瑞汽车股份有限公司 | Drying method of lithium ion battery pole pieces |
| CN103344097A (en) * | 2013-06-03 | 2013-10-09 | 奇瑞汽车股份有限公司 | Lithium ion battery cell drying method and lithium ion battery |
| CN104142045A (en) * | 2013-07-11 | 2014-11-12 | 中航锂电（洛阳）有限公司 | Method for drying cell of high-capacity lithium-ion battery |
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