CN108767171A - A method of for solving lithium ion battery dry method diaphragm fold - Google Patents
A method of for solving lithium ion battery dry method diaphragm fold Download PDFInfo
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- CN108767171A CN108767171A CN201810394322.7A CN201810394322A CN108767171A CN 108767171 A CN108767171 A CN 108767171A CN 201810394322 A CN201810394322 A CN 201810394322A CN 108767171 A CN108767171 A CN 108767171A
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- diaphragm
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- solvent
- processing pond
- lithium ion
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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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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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- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of methods for solving lithium ion battery dry method diaphragm fold, include the following steps of scheme one or scheme two：Scheme one：Solvent is poured into processing pond, maintains the constant and liquid level constant of processing pond temperature, the diaphragm before cutting is immersed in solvent, and diaphragm is made to pass through processing pond with constant walking speed, is then dried, after the completion of drying to obtain the final product；Scheme two：Solvent is poured into processing pond, maintains the constant and liquid level constant of processing pond temperature, the diaphragm before battery lamination or winding is immersed in solvent, and diaphragm is made to pass through processing pond with constant walking speed, is then dried, after the completion of drying to obtain the final product；The scheme one and the solvent in scheme two is identical or different.Of the present invention wider for solving method processing time of lithium ion battery dry method diaphragm fold, temperature controlling range, the selection face for handling solvent is wider, and the recyclable recycling of solvent, simple for process, relative maturity.
Description
Technical field
The invention belongs to field of lithium ion battery, more particularly, to one kind for solving lithium ion battery dry method diaphragm fold
Method.
Background technology
Constantly enhance recently as global energy conservation and environmental awareness, is representing the new-energy automobile of future automobile developing direction just
It is gradually received by consumer, industry development also gradually tends to be regular.In order to ensure that new-energy automobile has market competition for a long time
Power, upgrading drop are originally still entire industry and need the direction made joint efforts.Core component of the power battery as new-energy automobile,
The control of its cost is particularly important, and the diaphragm material as one of four big main materials is affected to battery overall price,
Middle dry method diaphragm has the good advantage of high in machining efficiency, of low cost and safety, market trend is more conform with, major
Battery Plant rises year by year using accounting.
Dry method list draws diaphragm in process, and longitudinal direction (MD), which occurs to stretch, to be orientated, and laterally the direction (TD) is then basic
It remains unchanged, therefore diaphragm has certain anisotropic, situations such as there are unbalanced stresses for process, later stage battery makes one
Denier completes fluid injection, and diaphragm is gradually discharged internal stress by organic solvent infiltration, and two facial differences further highlight, and the directions MD stress is released
Put bigger than normal compared with the directions TD, cell interface fixation at this time can not eliminate internal stress and fold occurs in time, and severe patient influences whole boundary
Surface evenness, and then influence battery performance and play.The present invention proposes a kind of process improving dry method diaphragm fold, main profit
Internal stress is discharged in advance with solvent infiltration diaphragm, avoids later stage fold from producing in battery processing completion early period diaphragm internal stresses release
It is raw, cell interface can be improved, to improve battery overall performance.
Dry method diaphragm buckling problems are commonplace at present, and also affecting the extensive of dry method diaphragm to a certain extent makes
With.Main cause is two anisotropy of dry method diaphragm, uneven in electrolyte impregnation process stress release and can not eliminate and cause in time
Fold.In order to improve dry method diaphragm buckling problems, diaphragm factory is improved using raw material adjustment, heat treatment, drawing process optimization
Strain problem, but the equal unobvious of the uneven improvement of membrane contacts electrolyte backward pull release；Each Battery Plant mainly passes through gel
Diaphragm and pole piece bonding are prevented stress release by technology, are firstly introduced into polymeric coating layer, and the manufacturing cost of diaphragm improves, next draws
Enter the heat pressing process of stringent temperature control, battery cost of manufacture improves, and last polymeric coating layer increases the internal resistance of cell, also has to electrical property
Certain adverse effect.
Invention content
In view of this, the present invention is directed to propose a kind of method for solving lithium ion battery dry method diaphragm fold, utilizes
Wettable solvent discharges diaphragm internal stress to the swelling action of diaphragm and the battery production later stage is avoided to generate fold in advance.
In order to achieve the above objectives, the technical proposal of the invention is realized in this way：
A method of for solving lithium ion battery dry method diaphragm fold, including the following step of scheme one or scheme two
Suddenly：
Scheme one：
Solvent is poured into processing pond, maintains the constant and liquid level constant of processing pond temperature, by before cutting every
Film immerses in solvent, and diaphragm is made to pass through processing pond with constant walking speed, is then dried, after the completion of drying to obtain the final product；
Scheme two：
Solvent is poured into processing pond, maintains the constant and liquid level constant of processing pond temperature, by battery lamination or
Diaphragm before winding immerses in solvent, and diaphragm is made to pass through processing pond with constant walking speed, is then dried, after the completion of drying
To obtain the final product；
The scheme one and the solvent in scheme two is identical or different.
For the treatment process of scheme one before diaphragm cutting, processing diaphragm state is parent roll.
For the treatment process of scheme two before battery lamination or winding, processing diaphragm state is product volume
Further, the temperature of the processing pond in the scheme one is 25 DEG C -100 DEG C, and the liquid level of processing pond is 1-
The walking speed of 3m, diaphragm are 5-100m/min, and the temperature of drying is 25 DEG C -120 DEG C, and the time of drying is 0.5-30min；It is preferred that
, the temperature of the processing pond in the scheme one is 50-80 DEG C, and the liquid level of processing pond is 2-2.5m, the walking speed of diaphragm
Temperature for 10-50m/min, drying is 80 DEG C -100 DEG C, and the time of drying is 1-5min.
Further, the width of the processing pond in the scheme one is 500-5000mm, length 500-10000mm, depth
Degree is 1.5-4m.
Further, the temperature of the processing pond in the scheme two is 20 DEG C -100 DEG C, and the liquid level of processing pond is
The walking speed of 0.2-1m, diaphragm are 20-100m/min, and the temperature of drying is 50 DEG C -120 DEG C, and the time of drying is 0.5-5min；It is excellent
Choosing, the temperature of the processing pond in the scheme two is 80-100 DEG C, and the liquid level of processing pond is 0.5-1.0m, diaphragm
Walking speed is 10-20m/min, and the temperature of drying is 90 DEG C -110 DEG C, and the time of drying is 0.5-2min.
Further, the width of the processing pond in the scheme two is 100-1000mm, length 100-1000mm, depth
For 0.5-1.5m.
Further, the solvent in the scheme one be dimethyl carbonate, dimethyl ether, carbon tetrachloride, chloroform,
At least one of trichloro ethylene, methyl ethyl carbonate, benzene, toluene or ethyl acetate；Preferably, the solvent in the scheme one
For at least one of dimethyl carbonate or methyl ethyl carbonate.
Further, the solvent in the scheme two be dimethyl carbonate, dimethyl ether, carbon tetrachloride, chloroform,
At least one of trichloro ethylene, methyl ethyl carbonate, benzene, toluene or ethyl acetate；Preferably, the solvent in the scheme two
For at least one of dimethyl carbonate or methyl ethyl carbonate.
The organic solvent in the preferred lithium-ion battery electrolytes of solvent in the scheme one.It can reduce to cell performance
It can influence.
The organic solvent in the preferred lithium-ion battery electrolytes of solvent in the scheme two.It can reduce to cell performance
It can influence.
Further, the surface tension of the solvent in the scheme one is 0-34 dynes, dielectric constant 0-21, and boiling point is
120℃-20℃；The surface tension of solvent in the scheme two is 0-34 dynes, dielectric constant 0-21, boiling point 120
℃-20℃。
Selected solvent is surface tension less than polypropylene (PP) and the relatively low low polar solvent of dielectric constant, surface
Power ensures that diaphragm impregnation process is smoothed out less than PP, and low-k ensures that solvent has PP materials certain swelling action,
It can quick release PP internal stress.Consider the solvent that technique realizability also needs selection boiling point relatively low, reduces and recycle
Energy consumption and high temperature are to diaphragm physicochemical property harmful effect.
Further, each step in the scheme two is sealed processing.
Two whole process of scheme requires encapsulation process, and processing pond floor space is smaller, and processing time shortens as possible not to be influenced
Battery processing efficiency.Some types diaphragm goes out the directions processing pond TD and has the dimensions variation, generally will increase, accurate before producing
Diaphragm size requirement is calculated, later stage diaphragm covering amount is avoided to fluctuate.Diaphragm goes out baking oven and carries out lamination and later stage production stage.
Scheme has certain environmental hazard, such as benzene, toluene just like the solvent of selection, then needs Recovery of Seal Oil to handle,
Avoid environmental pollution；Diaphragm cutting or coating and later stage production stage are carried out after drying.
Dry method diaphragm of the present invention is that dry method list draws diaphragm, dry method are double to draw diaphragm；Dry method single layer, bilayer, three layers and more
Layer diaphragm, wet method diaphragm and other types of diaphragms such as encounter unbalanced stress problem and the method improvement can also be used.Diaphragm width is wanted
50-5000mm, the directions MD intensity requirement >=50MPa, thermal contraction is asked to require 120 DEG C, 1h baking shrinking percentage≤5%
Compared with the existing technology, it is of the present invention for solve lithium ion battery dry method diaphragm fold method have with
Lower advantage：
(1) method of the present invention for solving lithium ion battery dry method diaphragm fold haves no need to change diaphragm raw material
And other processes, only need to introduce solvent treatment process, processing time, temperature controlling range are wider, handle the selection face of solvent compared with
Extensively, and the recyclable recycling of solvent, simple for process, relative maturity, production efficiency are higher.To the production efficiency of battery substantially without shadow
It rings.
(2) method of the present invention for solving lithium ion battery dry method diaphragm fold can increase to diaphragm processing
Before process cuts process, it can also increase to before cell processing course lamination process；This method principle is simple, equipment investment
Not high, solvent selects face wider, with obvious effects.
Description of the drawings
Fig. 1 is the cyclic curve figure of the embodiment of the present invention.
Specific implementation mode
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
With reference to embodiment and attached drawing, the present invention will be described in detail.
Embodiment 1
A method of for solving lithium ion battery dry method diaphragm fold, include the following steps：Methyl ethyl carbonate is fallen
Enter processing pond, processing pond width 3m, length 8m, depth 3m maintain processing pond temperature 70 C and liquid level 2m, diaphragm selection
PP material simple tension films, 16 μm of thickness；Solvent treatment process is before diaphragm cutting, and processing diaphragm state is parent roll, by diaphragm
It immerses in methyl ethyl carbonate, and diaphragm is made to pass through processing pond with walking speed 10m/min, handle total time 3min, then dried,
100 DEG C of drying temperature carries out cooling and standings 12h after diaphragm drying winding, is finally cut.
Cell positive material selects nickle cobalt lithium manganate tertiary cathode material, conductive agent to select carbon black class, binder selection poly-
Vinylidene fluoride film (PVDF), solvent select N-Methyl pyrrolidone (NMP)；Negative material selects artificial graphite, conductive agent choosing
Carbon black is selected, binder selects sodium carboxymethylcellulose (CMC), styrene-butadiene latex (SBR), solvent to select deionized water；Anode formula
NCM：Conductive agent：PVDF=95.5：2.5：2.0；Cathode formula artificial graphite：Conductive agent：CMC：SBR=96：1：1.5：1.5.
It is homogenized, is coated with according to old process, being rolled, Punching Technology；
Battery making is carried out using Z-shaped lamination process, carries out the processes such as fluid injection, preliminary filling, DEGAS, chemical conversion afterwards, it is last old
Change to stand and completes battery making.
Embodiment 2
A method of for solving lithium ion battery dry method diaphragm fold, include the following steps：By methyl ethyl carbonate, carbon
(mass ratio of methyl ethyl carbonate and dimethyl carbonate is 1 to dimethyl phthalate:1) processing pond is poured into, processing pond width 3m, length 8m,
Depth 3m maintains 70 DEG C of processing pond and 2m, diaphragm to select PP material simple tension films, and 16 μm of thickness, solvent treatment process exists
Before diaphragm cutting, processing diaphragm state is parent roll, and diaphragm is immersed in methyl ethyl carbonate, and keeps diaphragm logical with walking speed 10m/min
Processing pond is crossed, total time 3min is handled, is then dried, 100 DEG C of drying temperature, cooling and standings are carried out after diaphragm drying winding
12h is finally cut.
The formula of the positive electrode and negative electrode of battery and preparation method are same as Example 1.
Embodiment 3
A method of for solving lithium ion battery dry method diaphragm fold, include the following steps：By methyl ethyl carbonate, carbon
(mass ratio of methyl ethyl carbonate and dimethyl carbonate is 1 to dimethyl phthalate:1) processing pond, processing pond width 0.5m, length are poured into
1m, depth 1m maintain 80 DEG C of processing pond and liquid level 0.5m, diaphragm to select PP material simple tension films, 16 μm of thickness molten
For agent treatment process before battery Z-shaped lamination, processing diaphragm state is product volume, and diaphragm is immersed in methyl ethyl carbonate, and makes
Diaphragm by processing pond, is handled total time 45s, is then dried, 90 DEG C of drying temperature with walking speed 40m/min, go out baking oven into
Row Z-shaped lamination to obtain the final product.
The formula of the positive electrode and negative electrode of battery and preparation method are same as Example 1.
Comparative example 1
Specification, the batch all same of diaphragm and embodiment 1, but handle without solvent and directly cut for use, battery is just
The formula of pole and cathode is same as Example 1 with preparation method, the formulas of the positive electrode and negative electrode of battery and preparation method with
Embodiment 1 is identical.
Evaluation and test project：
1. 1 battery average thickness of testing example 1-3 and comparative example；
2. embodiment 1-3 and 1 battery of comparative example are carried out 100%SOC state dismantlings, diaphragm fold situation is observed；
3. embodiment 1-3 and 1 battery of comparative example are carried out 55 DEG C of high temperature circulation tests, observation capacity keeps situation.
Related evaluation result is as follows, and embodiment 1-3 discharges diaphragm internal stress by solvent advanced processing diaphragm, can be effective
Improving diaphragm buckling problems, reduce cell thickness, maintains interface smooth, embodiment 1-3 batteries embody good cycle performance,
The results are shown in Figure 1.Three embodiment comparisons, more preferably, battery 100%SOC states disassemble result to the scheme works of solvent mixture
It is as shown in table 1 with thickness.
Table 1：100%SOC state batteries disassemble situation
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
With within principle, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention god.
Claims (9)
1. a kind of method for solving lithium ion battery dry method diaphragm fold, it is characterised in that：Including scheme one or scheme two
Following steps：
Scheme one：
Solvent is poured into processing pond, maintains the constant and liquid level constant of processing pond temperature, the diaphragm before cutting is soaked
Enter in solvent, and diaphragm is made to pass through processing pond with constant walking speed, then dried, after the completion of drying to obtain the final product；
Scheme two：
Solvent is poured into processing pond, the constant and liquid level constant of processing pond temperature is maintained, by battery lamination or winding
Preceding diaphragm immerses in solvent, and diaphragm is made to pass through processing pond with constant walking speed, is then dried, after the completion of drying i.e.
?；
The scheme one and the solvent in scheme two is identical or different.
2. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme one in the temperature of processing pond be 25 DEG C -100 DEG C, the liquid level of processing pond is 1-3m, and the walking speed of diaphragm is 5-
The temperature of 100m/min, drying are 25 DEG C -120 DEG C, and the time of drying is 0.5-30min；Preferably, in the scheme one
The temperature of processing pond is 50-80 DEG C, and the liquid level of processing pond is 2-2.5m, and the walking speed of diaphragm is 10-50m/min, drying
Temperature is 80 DEG C -100 DEG C, and the time of drying is 1-5min.
3. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme one in processing pond width be 500-5000mm, length 500-10000mm, depth 1.5-4m.
4. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme two in the temperature of processing pond be 20 DEG C -100 DEG C, the liquid level of processing pond is 0.2-1m, and the walking speed of diaphragm is 20-
The temperature of 100m/min, drying are 50 DEG C -120 DEG C, and the time of drying is 0.5-5min；Preferably, in the scheme two
The temperature of processing pond is 80-100 DEG C, and the liquid level of processing pond is 0.5-1.0m, and the walking speed of diaphragm is 10-20m/min, drying
Temperature be 90 DEG C -110 DEG C, time of drying is 0.5-2min.
5. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme two in processing pond width be 100-1000mm, length 100-1000mm, depth 0.5-1.5m.
6. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme one in solvent be dimethyl carbonate, dimethyl ether, carbon tetrachloride, chloroform, trichloro ethylene, methyl ethyl carbonate
At least one of ester, benzene, toluene or ethyl acetate；Preferably, the solvent in the scheme one is dimethyl carbonate or carbon
At least one of sour methyl ethyl ester.
7. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme two in solvent be dimethyl carbonate, dimethyl ether, carbon tetrachloride, chloroform, trichloro ethylene, methyl ethyl carbonate
At least one of ester, benzene, toluene or ethyl acetate；Preferably, the solvent in the scheme two is dimethyl carbonate or carbon
At least one of sour methyl ethyl ester.
8. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme one in solvent surface tension be 0-34 dynes, dielectric constant 0-21, boiling point be 120 DEG C -20 DEG C；The side
The surface tension of solvent in case two is 0-34 dynes, dielectric constant 0-21, and boiling point is 120 DEG C -20 DEG C.
9. the method according to claim 1 for solving lithium ion battery dry method diaphragm fold, it is characterised in that：It is described
Scheme two in each step be sealed processing.
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| CN201810394322.7A CN108767171A (en) | 2018-04-27 | 2018-04-27 | A method of for solving lithium ion battery dry method diaphragm fold |
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|---|---|---|---|
| CN201810394322.7A CN108767171A (en) | 2018-04-27 | 2018-04-27 | A method of for solving lithium ion battery dry method diaphragm fold |
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Citations (3)
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|---|---|---|---|---|
| CN103337602B (en) * | 2013-06-26 | 2015-05-13 | 宁德新能源科技有限公司 | Isolating film and electrochemical device |
| KR20170059495A (en) * | 2015-11-20 | 2017-05-31 | 유펙스켐(주) | Apparatus of manufacturing battery separator |
| CN107749451A (en) * | 2017-10-21 | 2018-03-02 | 湖南中锂新材料科技有限公司 | A kind of preparation method of low stress lithium ion battery separator |
-
2018
- 2018-04-27 CN CN201810394322.7A patent/CN108767171A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103337602B (en) * | 2013-06-26 | 2015-05-13 | 宁德新能源科技有限公司 | Isolating film and electrochemical device |
| KR20170059495A (en) * | 2015-11-20 | 2017-05-31 | 유펙스켐(주) | Apparatus of manufacturing battery separator |
| CN107749451A (en) * | 2017-10-21 | 2018-03-02 | 湖南中锂新材料科技有限公司 | A kind of preparation method of low stress lithium ion battery separator |
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| 曹炳炎: "《石油化工读物手册》", 31 December 1992 * |
| 程能林: "《溶剂手册 第二版》", 31 December 1994 * |
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Application publication date: 20181106 |