CN101635351B - Method for producing one-sided film pole piece for lithium secondary battery - Google Patents
Method for producing one-sided film pole piece for lithium secondary battery Download PDFInfo
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- CN101635351B CN101635351B CN2009103007938A CN200910300793A CN101635351B CN 101635351 B CN101635351 B CN 101635351B CN 2009103007938 A CN2009103007938 A CN 2009103007938A CN 200910300793 A CN200910300793 A CN 200910300793A CN 101635351 B CN101635351 B CN 101635351B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a method for producing a one-sided film pole piece for a lithium secondary battery, which comprises the following steps: sequentially coating, drying and rolling a metal substrate, wherein the coating process is one side coating, and crystalline flake graphite is added to anode materials and cathode materials for coating; and the coated and dried substrate is folded or two layers of one-sided film substrates are overlapped to enable the uncoated metal foil surfaces opposite to each other and then rolling process is followed. The invention effectively solves the problem of severe coiling of the one-sided film pole piece for the lithium secondary battery in the manufacturing process. The one-sided film pole piece can be widely used for the model design of the lithium secondary battery. The one-sided film pole piece can be used for reducing the thickness of the lithium battery, increasing the energy density of the lithium battery and reducing the cost of the battery, and is especially suitable for producing ultra-thin polymer (flexible packing) lithium batteries.
Description
Technical field
The present invention relates to lithium ion battery, be specifically related to a kind of production method of one-sided film pole piece for lithium secondary battery.
Background technology
The lithium secondary battery positive and negative plate technological process of production is at present: at first be that negative or positive electrode powder, conductive agent, solvent, binding agent etc. are mixed with into the finely dispersed slurry of solid-liquid two-phase, then slurry is coated in two surfaces of metal forming, then do oven dry and handle and roll processing, cut again that moulding is laggard goes into the battery assembling procedure.Wherein pole piece rolls flow process as shown in Figure 1.
Along with the lithium secondary battery application is more and more wider, market requires more and more diversified to it, for example reduces thickness, improves energy density and ultrathin polymer (flexible package) lithium battery.So just having expedited the emergence of a kind of new pole piece structural design, mainly is to process the pole piece that only applies the single face film.
Processing technology according to present lithium battery routine, pole piece must be rolled, with the caking property of the density that improves active material and itself and metal foil, if do not roll pole piece could cause that the finished product internal resistance of cell is very big, performances such as battery capacity and circulation reduce greatly even can't use.The roller that the lithium battery industry is used at present all adopts pressure roller, pressurization, rotating manner, pole piece is that the linear surface short time is stressed in the process of rolling, because metal foil calendering characteristic is different with the superincumbent positive and negative pole material calendering of coating characteristic, stressed end back bounce-back situation is also inequality, so only applying the pole piece of single face film all can curl towards the metal foil surface direction after rolling, have a strong impact on the following process of pole piece, increase the production operation difficulty and maybe can't operate (as shown in Figure 2).It is curling very serious that one-sided film pole piece rolls the back pole piece, also makes the pole piece of this type of structural design and ultrathin polymer (flexible package) battery can't realize large-scale production.
Over past ten years, the secondary cell of China especially lithium secondary battery output increases fast, and output and scale have occupy prostatitis, the world.But in aspect and external big in addition gaps such as for example cylindrical electrokinetic cell in high-end battery technology field, polymer battery, ultra-thin batteries.As present extra-thin chemical cell, a lot of application are arranged in practice, such as at c bookmart, small electronic apparatus, music New Year card and birthday card have the initiatively credit card and the bank card of power supply, the application during freight transportation on signal emitting-source of location tracking monitoring or the like product.Present extra-thin chemical cell has only united states, japan and other countries man's minority major company to grasp this technology basically, and ultrathin lithium battery is domestic to rarely have production especially.If can solve the curling problem that one-sided film pole piece processing exists, also can make the large-scale production of ultrathin polymer (flexible package) lithium battery become possibility.
Roll the serious problem of curling that produces of handling for solving substrate, existing solution concentrates on mostly and is coated with in the membrane process, provide the method for pole piece coating as Chinese patent application CN200610061106.8, CN 200710185231.4, to obtain to film uniform pole piece; CN200810066074 discloses a kind of manufacture method of anode slice of lithium ion battery, mainly solve the bonding adhesive force problem of filming, thereby improve the pole piece processing characteristics, but these method operating process are more loaded down with trivial details, nor are to be coated with film pole piece production efficient ways at single face.Therefore, lack the special production method that solves one-sided film pole piece for lithium secondary battery in the prior art.
Summary of the invention
For effectively solving the problem that prior art exists; the present invention proposes a kind of mode and film-making technological process of placing substrate when need changing linear roll-in; adjust simultaneously suitably the material prescription of coated rete and the technological parameter when rolling; just can reduce the amount of crimp of substrate greatly, can accomplish scale production thereby the feasible lithium battery of using one-sided film pole piece comprises ultrathin polymer (flexible package) lithium battery.
The objective of the invention is to be implemented by the following technical programs:
A kind of production method of one-sided film pole piece for lithium secondary battery, described production method are substrate to be taken turns doing film, dry, roll processing, and wherein, described filming filmed for single face, add crystalline flake graphite in the positive and negative electrode material that adopts of filming; The substrate of filming oven dry back doubling or two substrates be overlapping to be made not coated surface do relatively to roll processing again.
Additive--special graphite is crystalline flake graphite in adding in the positive and negative pole material prescription, and this graphite-structure is the fish scale sheet.Because positive and negative pole material and electrically conductive graphite etc. are sphere or class ball-type structure mostly, after adding the fish scale flake graphite, flaky graphite has the ability of parallel sliding and fills position, space between the microcosmic sphere material when rolling, and the stress that makes the material of ball-type structure produce when rolling reduces greatly.Roll and finish back bounce-back situation and alleviate so be added with the one-sided film pole piece of an amount of crystalline flake graphite additive, can effectively reduce pole piece and curl.This additive and electrically conductive graphite are with a kind of chemical composition-C (carbon) simultaneously, and just structure has difference, so can not influence any performance of battery again when adding this additive.
When rolling, the doubling of single face film substrate or two layers of one-sided film substrate are rolled after overlapping together simultaneously, make the metal covering of not filming relative when overlapping.Make covert the becoming of single face film substrate " double-side membrane substrate " roll like this, in the process of rolling, effectively alleviate the substrate amount of crimp and be beneficial to roll continuously production, obtain qualified pole piece.
As preferably, according to production method of the present invention, wherein, described crystalline flake graphite accounts for the 0.5-3% of positive and negative electrode material weight.
As preferably, according to production method of the present invention, wherein, described positive electrode is by the PVDF(Kynoar of the electrically conductive graphite of at least a, the 1～5wt% in the cobalt of 90～95wt% acid lithium, lithium nickelate, LiFePO4, LiMn2O4 and the ternary material etc., 0.5～3wt% crystalline flake graphite and 2～5%) form.
As preferably, according to production method of the present invention, wherein, described negative material is formed 2～5% PVDF by the crystalline flake graphite of the electrically conductive graphite of the composite graphite of 90～95wt%, 1～5wt%, 0.5～3wt% or the composition of 1～1.5%CMC (carboxymethyl cellulose) and 2～3%SBR (styrene butadiene rubber) is formed.
As preferably, according to production method of the present invention, wherein roll and the doubling of single face film substrate or two layers of one-sided film substrate are rolled after overlapping together before handling, make the metal covering of not filming relative when overlapping, corresponding simultaneously rete also will align (as shown in Figure 6).
As preferably, according to production method of the present invention, wherein, described roll the technological parameter that rolls in the processing be rolling speed be 4-6 rice/minute; Compacted density is that anodal one-sided film pole piece is at 2.0-3.6g/cm
3, cathode pole piece is 1.2-1.5g/cm
3
Corresponding adjusting process parameter when rolling one-sided film pole piece comprises and reduces rolling speed to 4～6 meters of per minutes (conventional double-side membrane pole piece technological parameter is more than 10 meters) that the compacted density that reduces pole piece is to anodal one-sided film pole piece 2.0～3.6g/cm
3, negative pole one-sided film pole piece 1.2～1.5g/cm
3(conventional double-side membrane pole piece technological parameter technological parameter is anode pole piece 2.3～4.0g/cm
3, cathode pole piece 1.6～1.7g/cm
3), so not only can guarantee battery performance, also farthest reduce the internal stress of the process of rolling, be beneficial to alleviate pole piece and curl.
As preferably, according to production method of the present invention, wherein, described substrate is Copper Foil or aluminium foil, and its thickness is between 9～20 μ m.
As preferably, according to production method of the present invention, wherein, the thick 50-150 μ m of being of rete in the described processing of filming.
As preferably, according to production method of the present invention, wherein, described rolling adopted roll squeezer in the processing, and moulding pressure is 10-100T(1T=1000kg, usually 1MPa=10kg.), temperature is 5-40 ℃, revolution is 0.5-5r/min.
As preferably, according to production method of the present invention, wherein, described production method also comprises rolling to do after the processing and cuts forming processes.
One-sided film pole piece work flow provided by the invention generally comprises (as shown in Figure 3): at first negative or positive electrode powder, solvent, binding agent, additive are mixed with into the finely dispersed slurry of solid-liquid two-phase, then slurry is coated on the surface of metal aluminum foil and Copper Foil and does oven dry and handle, before rolling that one-sided film pole piece doubling or two one-sided film pole pieces is overlapping, the metal forming foil of one-sided film pole piece surface relatively when overlapping, corresponding rete also will align, again do and roll processing, can obtain required one-sided film pole piece thereafter.Can enter the assembled battery operation after the one-sided film pole piece of gained cut moulding again.
Compared with prior art, the present invention has the following advantages:
The present invention can solve one-sided film pole piece and rolls in the processing and to produce serious curling, so that problem that can't ordinary production has very actual and wide application in the lithium secondary battery design with in producing.For example, in the square stacked lithium battery of each gauge size, use two single face film positive plates and start and finish up, not only can reduce cell thickness, improve energy density, can also reduce the consumption of two barrier films and a slice Copper Foil.Because barrier film and Copper Foil proportion in the lithium battery cost higher (generally speaking 20～35%) can also reduce production costs by a relatively large margin so use one-sided film pole piece.Again for example, when producing extra-thin polymer (flexible package) lithium battery, owing to want to use one-sided film pole piece, and common process can't process qualified one-sided film pole piece, can guarantee pole piece production and product quality requirement after using the present invention, so the technology of the present invention seems even more important in the application aspect the ultrathin lithium battery.
Description of drawings
Fig. 1 rolls schematic flow sheet in the conventional lithium battery pole slice processing of prior art;
Fig. 2 is that the prior art lithium battery is processed schematic diagram with one-sided film pole piece;
Fig. 3 is that lithium battery of the present invention is processed schematic diagram with one-sided film pole piece;
Fig. 4 is that the embodiment of the invention 1 is coated with the membrane process schematic diagram;
Fig. 5 stacks schematic diagram before 1 two one-sided film pole pieces of the embodiment of the invention roll processing;
Fig. 6 is that the embodiment of the invention 1 stacks latter two one-sided film pole piece and rolls the processing schematic diagram;
Fig. 7 is that 2 one one-sided film pole pieces of the embodiment of the invention roll the preceding doubling schematic diagram of processing;
Fig. 8 rolls the processing schematic diagram after 2 one one-sided film pole piece doublings of the embodiment of the invention.
Embodiment
Below in conjunction with embodiment, be described more specifically content of the present invention.Should be appreciated that enforcement of the present invention is not limited to the following examples, all will fall into protection range of the present invention any pro forma accommodation and/or the change that the present invention made.
In the present invention, if not refer in particular to, all part, percentages are unit of weight, and all equipment and raw material etc. all can be buied from market or the industry is commonly used.Copper Foil or aluminium foil are prepared according to the specification of 9-20 μ m, are coated with in the membrane process film thickness monitoring at 50-150 μ m.
Embodiment 1
According to preparing the positive and negative electrode raw material in table 1 and the table 2 shown in the prescription 1, and add solvent and prepare the solid-liquid two-phase according to conventional method and mix finely dispersed positive and negative electrode slurry.
The positive and negative electrode slurry of preparation is coated on the surface of metal aluminum foil (as shown in Figure 4) oven dry then respectively.Get two volume one-sided film pole piece volumes, two volume one-sided film pole pieces are stacked (as shown in Figure 5), make that the metal foil surfaces of two volume one-sided film pole pieces is relative, corresponding simultaneously rete also will align.The two volume one-sided film pole pieces volumes that will stack are then sent into and are rolled processing (as shown in Figure 6) in the roller, and the compaction technology parameter is: rolling speed be 4-6 rice/minute, anodal one-sided film pole piece compacted density is 2.0-3.6g/cm
3, negative pole one-sided film pole piece compacted density is 1.2-1.5g/cm
3, moulding pressure 10-100T rolls temperature 5-40 ℃, roller rotating speed 0.5-5r/min.Roll finish after respectively with the one-sided film pole piece rolling, cut moulding, enter next step operation assembled battery.
Embodiment 2
According to preparing the positive and negative electrode raw material in table 1 and the table 2 shown in the prescription 2, and add solvent and prepare the solid-liquid two-phase according to conventional method and mix finely dispersed positive and negative electrode slurry.
The positive and negative electrode slurry of preparation is coated on the surface of metal copper foil (as shown in Figure 4) oven dry then respectively.Get two and roll the one-sided film pole piece volume that is equipped with, two volume one-sided film pole pieces are stacked (as shown in Figure 5), make that the metal foil surfaces of two volume one-sided film pole pieces is relative, corresponding simultaneously rete also will align.The two volume one-sided film pole pieces volumes that will stack are then sent into and are rolled processing (as shown in Figure 6) in the roller, and the compaction technology parameter is: rolling speed be 4-6 rice/minute, anodal one-sided film pole piece compacted density is 2.0-3.6g/cm
3, negative pole one-sided film pole piece compacted density is 1.2-1.5g/cm
3, moulding pressure 10-100T rolls temperature 5-40 ℃, roller rotating speed 0.5-5r/min.Roll finish after respectively with the one-sided film pole piece rolling, cut moulding, enter next step operation assembled battery.
Embodiment 3
According to preparing the positive and negative electrode raw material in table 1 and the table 2 shown in the prescription 3, and add solvent and prepare the solid-liquid two-phase according to conventional method and mix finely dispersed positive and negative electrode slurry.
The positive and negative electrode slurry of preparation is coated on the surface of metal aluminum foil (as shown in Figure 4) oven dry then respectively.Get one and roll the one-sided film pole piece volume that is equipped with, with its doubling (as shown in Figure 7), make that the metal foil surfaces of one-sided film pole piece is relative, corresponding simultaneously rete also will align.To send into the one-sided film pole piece rolled well volume then and roll processing (as shown in Figure 8) in the roller, the compaction technology parameter is: rolling speed be 4-6 rice/minute, anodal one-sided film pole piece compacted density is 2.0-3.6g/cm
3, negative pole one-sided film pole piece compacted density is 1.2-1.5g/cm
3, moulding pressure 10-100T rolls temperature 5-40 ℃, roller rotating speed 0.5-5r/min.Roll finish after with the one-sided film pole piece rolling, cut moulding, enter next step operation assembled battery.
Embodiment 4
According to preparing the positive and negative electrode raw material in table 1 and the table 2 shown in the prescription 4, and add solvent and prepare the solid-liquid two-phase according to conventional method and mix finely dispersed positive and negative electrode slurry.
The positive and negative electrode slurry of preparation is coated on the surface of metal copper foil (as shown in Figure 4) oven dry then respectively.Get one and roll the one-sided film pole piece volume that is equipped with, with its doubling (as shown in Figure 7), make that the metal foil surfaces of two volume one-sided film pole pieces is relative, corresponding simultaneously rete also will align.To send into the one-sided film pole piece rolled well volume then and roll processing (as shown in Figure 8) in the roller, the compaction technology parameter is: rolling speed be 4-6 rice/minute, anodal one-sided film pole piece compacted density is 2.0-3.6g/cm
3, negative pole one-sided film pole piece compacted density is 1.2-1.5g/cm
3, moulding pressure 10-100T rolls temperature 5-40 ℃, roller rotating speed 0.5-5r/min.Roll finish after with the one-sided film pole piece rolling, cut moulding, enter next step operation assembled battery.
Embodiment 5
According to preparing the positive and negative electrode raw material in table 1 and the table 2 shown in the prescription 5, and add solvent and prepare the solid-liquid two-phase according to conventional method and mix finely dispersed positive and negative electrode slurry.
Other operations are with embodiment 1.
Embodiment 6
According to preparing the positive and negative electrode raw material in table 1 and the table 2 shown in the prescription 6, and add solvent and prepare the solid-liquid two-phase according to conventional method and mix finely dispersed positive and negative electrode slurry.
Other operations are with embodiment 3.
Application examples 2The one-sided film pole piece of the inventive method preparation is used for ultrathin polymer (flexible package) lithium battery
By top application examples as can be seen, if the square poly-lithium battery of same capability uses the one-sided film pole piece of the present invention's preparation, cell thickness can reduce 3～15%, and the thickness effect that the battery that capacity is more little reduces is obvious more.
Especially ultrathin polymer (flexible package) lithium battery must use one-sided film pole piece, and its effect that reduces cell thickness is more obvious.
Simultaneously by also seeing in the table, because can reduce the higher raw-material use amounts of price such as Copper Foil and barrier film, so also can reduce production costs.
Claims (9)
1. the production method of an one-sided film pole piece for lithium secondary battery, described production method is substrate to be taken turns doing film, dry, roll processing, it is characterized in that, described filming filmed for single face, filming adds crystalline flake graphite in the positive and negative electrode material that adopts, and described crystalline flake graphite accounts for the 0.5-3wt% of positive and negative electrode material weight; The substrate of filming oven dry back doubling or two substrates be overlapping to be made not coated surface do relatively to roll processing again.
2. production method as claimed in claim 1, it is characterized in that described positive electrode is made up of at least a, the electrically conductive graphite of 1～5wt% in the cobalt of 90～95wt% acid lithium, lithium nickelate, LiFePO4, LiMn2O4 and the ternary material, the crystalline flake graphite of 0.5～3wt%, the PVDF of 2～5wt%.
3. production method as claimed in claim 1, it is characterized in that described negative material is made up of the PVDF of the crystalline flake graphite of the electrically conductive graphite of at least a, the 1～5wt% in composite graphite, Delanium, native graphite and the modified natural graphite of 90～95wt%, 0.5～3wt%, 2～5wt% or 1～2wt%CMC and 1.5～3wt%SBR composition.
4. production method as claimed in claim 1 is characterized in that, described rolling rolled the doubling of single face film substrate or two substrates after overlapping before handling together again, makes when overlapping that coated surface is not relative, and corresponding simultaneously rete film also will align.
5. production method as claimed in claim 1 is characterized in that, described roll in the processing compaction technology parameter be rolling speed be 4-6 rice/minute; The anodal one-sided film pole piece of compacted density is at 2.0-3.6g/cm
3, the negative pole one-sided film pole piece is at 1.2-1.5g/cm
3
6. production method as claimed in claim 1 is characterized in that, described substrate is Copper Foil or aluminium foil, and its thickness is at 9～20 μ m.
7. production method as claimed in claim 1 is characterized in that, thickness is 50-150 μ m in the described processing of filming.
8. production method as claimed in claim 1 is characterized in that, described rolling adopted roll squeezer in the processing, and moulding pressure is 10-100T, and temperature is 5-40 ℃, and revolution is 0.5-5r/min.
9. production method as claimed in claim 1 is characterized in that, described production method also comprises rolling to do after the processing and cuts forming processes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103007938A CN101635351B (en) | 2009-03-11 | 2009-03-11 | Method for producing one-sided film pole piece for lithium secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103007938A CN101635351B (en) | 2009-03-11 | 2009-03-11 | Method for producing one-sided film pole piece for lithium secondary battery |
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| CN101635351A CN101635351A (en) | 2010-01-27 |
| CN101635351B true CN101635351B (en) | 2011-01-26 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5961922B2 (en) * | 2010-05-31 | 2016-08-03 | 日産自動車株式会社 | Negative electrode for secondary battery and method for producing the same |
| CN102064312A (en) * | 2010-12-13 | 2011-05-18 | 湖南科力远新能源股份有限公司 | Manufacturing methods of secondary battery negative electrode slice, negative electrode and secondary battery, and secondary battery manufactured by same |
| JP5855483B2 (en) * | 2012-02-13 | 2016-02-09 | 日産自動車株式会社 | Battery pressing device and battery pressing method |
| CN103296252A (en) * | 2013-06-13 | 2013-09-11 | 高平唐一新能源科技有限公司 | Device for preventing upwarping of lithium battery coating pole piece |
| CN116364863B (en) * | 2023-06-02 | 2023-10-03 | 新乡市弘力电源科技有限公司 | Dry electrode preparation device for lithium ion battery |
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