CN105576178A - Wet nonwoven fabric ceramic diaphragm of lithium ion power battery and preparation method thereof - Google Patents
Wet nonwoven fabric ceramic diaphragm of lithium ion power battery and preparation method thereof Download PDFInfo
- Publication number
- CN105576178A CN105576178A CN201610110894.9A CN201610110894A CN105576178A CN 105576178 A CN105576178 A CN 105576178A CN 201610110894 A CN201610110894 A CN 201610110894A CN 105576178 A CN105576178 A CN 105576178A
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- Prior art keywords
- ceramic
- ceramic diaphragm
- wet nonwoven
- nonwoven fabric
- diaphragm
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Cell Separators (AREA)
Abstract
The invention discloses a wet nonwoven fabric ceramic diaphragm of a lithium ion power battery and a preparation method of the wet nonwoven fabric ceramic diaphragm. The wet nonwoven fabric ceramic diaphragm is formed by a substrate and a single-surface or double-surface coating layer, wherein the substrate is wet nonwoven fabric; the coating layer is obtained by coating the surface of the substrate with a ceramic solution. The preparation method of the wet nonwoven fabric ceramic diaphragm comprises the following steps of firstly preparing the ceramic solution, and then coating the surface of the substrate with the ceramic solution, thus obtaining the wet nonwoven fabric ceramic diaphragm of the lithium ion power battery. The wet nonwoven fabric ceramic diaphragm disclosed by the invention has the advantages that the porosity is ideal, the ion migration speed is quick, the permeability speed of electrolyte during liquid injection is quick, and the production efficiency is high; the temperature resistance is good, the preparation operation is simple, and the energy consumption is low; the wet nonwoven fabric ceramic diaphragm has high temperature resistance and low shrink, the wet nonwoven fabric ceramic diaphragm cannot shrink immediately when the wet nonwoven fabric ceramic diaphragm is in short circuit as being impaled by a hard matter, and the lithium ion power battery is prevented from burning as the lithium ion power battery is in large-area contact with oxygen.
Description
Technical field
Wet nonwoven fabrics ceramic diaphragm that the present invention relates to a kind of lithium-ion-power cell and preparation method thereof.
Background technology
At present, common on market lithium ion battery separator mainly comprises: organic polymer class barrier film and single or multiple lift ceramic diaphragm.Organic polymer class barrier film mainly comprises polyethylene film, polypropylene screen etc., poor heat resistance, the porosity of this kind of barrier film are low, and easy temperature distortion causes both positive and negative polarity to contact with each other and internal short-circuit occurs, finally may there is thermal runaway or blast, there is very large secret worry at secure context.Meanwhile, due to the restriction by preparation technology, after this kind of barrier film is pierced through by hard object, irreversible injury can be suffered.The ceramic powder that ceramic diaphragm is conventional is nano alumina particles, owing to easily reuniting between alumina particle, form larger agglomerated particle, therefore often there is dry linting and the problem such as uniformity is low, harmful effect is produced to follow-up coating process, meanwhile, the easy block micro pores film of alumina particle of nano shape, barrier effect is caused to the migration of ion, the problems such as final generation thermal runaway.
Along with the development of science and technology and the progress of society, market is more and more ardenter to the demand of electrokinetic cell, therefore needs a kind of new types of diaphragm that can be used for power lithium-ion battery of exploitation badly, to meet the growing market demand.
Summary of the invention
Wet nonwoven fabrics ceramic diaphragm that the object of the present invention is to provide a kind of lithium-ion-power cell and preparation method thereof.
The technical solution used in the present invention is:
A kind of wet nonwoven fabrics ceramic diaphragm of lithium-ion-power cell is by base material and one side or coated on both sides forms, and described base material is wet nonwoven fabrics, and described coating obtains by ceramic solution is coated to substrate surface.
Described wet nonwoven fabrics is surface density 6 ~ 10g/m
2, 10 ~ 15g/m
2, 15 ~ 25g/m
2nonwoven fabrics in one.
The thickness of described base material is 12 ~ 15 μm.
The thickness of described coating is 12 ~ 15 μm.
Described ceramic solution is made up of the raw material of following mass percentage: ceramic powder: 20% ~ 25%; Carboxymethyl cellulose: 1% ~ 3%; Butadiene-styrene rubber: 7% ~ 18%; Surplus is water.
The particle diameter of described ceramic powder is 1 ~ 5 μm.
Described ceramic powder is SiO
2, Al
2o
3, Al (OH) 3, TiO
2, ZrO
2, at least one in MgO, SiC.
The preparation method of described ceramic diaphragm, comprises the following steps: first prepare ceramic solution, then ceramic solution is coated to matrix surface, namely obtains the wet nonwoven fabrics ceramic diaphragm of lithium-ion-power cell.
Method ceramic solution being coated to matrix surface is at least one in nick coating, extrusion coated, dip-coating, spraying.
The invention has the beneficial effects as follows:
(1) wet nonwoven fabrics ceramic diaphragm of the present invention has desirable porosity, and Ion transfer speed is fast, and during fluid injection, the seepage velocity of electrolyte is fast, improves production efficiency;
(2) wet nonwoven fabrics ceramic diaphragm of the present invention has good temperature tolerance, and when power lithium-ion battery high rate charge-discharge, the high temperature that inside battery produces can not have an impact to battery efficiency;
(3) wet nonwoven fabrics ceramic diaphragm of the present invention has good temperature tolerance, in battery manufacturing process, can operate, decrease battery baking time, simplify operation, saved the energy, improve production efficiency at 110 ~ 120 DEG C;
(4) high temperature resistant, the lower shrinkage of wet nonwoven fabrics ceramic diaphragm of the present invention, when barrier film by hard object pierce through be short-circuited time, barrier film also can not shrink immediately, avoids battery and burns on fire because of bump contact oxygen.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the ceramic diaphragm of embodiment 1.
Fig. 2 is the contraction test comparison figure of the ceramic diaphragm of polypropylene diaphragm, polyethylene ceramic diaphragm, polypropylene ceramic diaphragm and embodiment 1.
Fig. 3 is 55 DEG C of charge-discharge test Comparative result figure of the full battery of 15Ah prepared with the ceramic diaphragm of import PP ceramic diaphragm and embodiment 1.
Fig. 4 is the room temperature charge-discharge test Comparative result figure of the full battery of 20Ah prepared with the ceramic diaphragm of import PP ceramic diaphragm and embodiment 1.
Fig. 5 is 15Ah battery 80 DEG C of discharge tests of the ceramic diaphragm of import PP ceramic diaphragm and embodiment 1 and replys volume test Comparative result figure.
Embodiment
A kind of wet nonwoven fabrics ceramic diaphragm of lithium-ion-power cell is by base material and one side or coated on both sides forms, and described base material is wet nonwoven fabrics, and described coating obtains by ceramic solution is coated to substrate surface.
Preferably, described wet nonwoven fabrics is surface density 6 ~ 10g/m
2, 10 ~ 15g/m
2, 15 ~ 25g/m
2nonwoven fabrics in one.
Preferably, the thickness of described base material is 12 ~ 15 μm.
Preferably, the thickness of described coating is 12 ~ 15 μm.
Preferably, described ceramic solution is made up of the raw material of following mass percentage: ceramic powder: 20% ~ 25%; Carboxymethyl cellulose: 1% ~ 3%; Butadiene-styrene rubber: 7% ~ 18%; Surplus is water.
Preferably, the particle diameter of described ceramic powder is 1 ~ 5 μm.
Preferably, described ceramic powder is SiO
2, Al
2o
3, Al (OH) 3, TiO
2, ZrO
2, at least one in MgO, SiC.
The preparation method of described ceramic diaphragm, comprises the following steps: first prepare ceramic solution, then ceramic solution is coated to matrix surface, namely obtains the wet nonwoven fabrics ceramic diaphragm of lithium-ion-power cell.
Preferably, method ceramic solution being coated to matrix surface is at least one in nick coating, extrusion coated, dip-coating, spraying.
Below in conjunction with specific embodiment, the present invention is made further explanation and description.
embodiment 1:
Select surface density 6 ~ 10g/m
2wet nonwoven fabrics as base material; In the ceramic solution of preparation, the mass percentage of each raw material is as follows: ceramic powder (SiO
2): 20%; Carboxymethyl cellulose: 2%; Butadiene-styrene rubber 8%; Deionized water: 70%.
Ceramic solution is coated in wet nonwoven fabrics substrate surface by the mode of extrusion coated, dry, namely obtain ceramic diaphragm.
As shown in Figure 1, the SEM that wherein (a) is this ceramic diaphragm front schemes the SEM figure of ceramic diaphragm prepared by the present embodiment, and the SEM that (b) is this ceramic diaphragm cross section schemes.
The contraction test comparison figure of ceramic diaphragm prepared by polypropylene diaphragm, polyethylene ceramic diaphragm, polypropylene ceramic diaphragm and the present embodiment as shown in Figure 2, wherein (a) is polypropylene diaphragm (PP), b () is polyethylene ceramic diaphragm (PE+Mg), c () is polypropylene ceramic diaphragm (PP+Al), d ceramic diaphragm that () prepares for the present embodiment, test condition is: 200 DEG C of constant temperature baking 30min.
The ceramic diaphragm of import PP ceramic diaphragm and embodiment 1 is made the full battery of 15Ah, at 55 DEG C, carries out 1C charge-discharge test, as shown in Figure 3, wherein: NW is ceramic diaphragm prepared by the present embodiment, PP is import PP ceramic diaphragm to its test result.
The ceramic diaphragm of import PP ceramic diaphragm and embodiment 1 is made the full battery of 20Ah, and at room temperature carrying out 1C charge-discharge test, as shown in Figure 4, wherein: NW is ceramic diaphragm prepared by the present embodiment, PP is import PP ceramic diaphragm to its test result.
The ceramic diaphragm of import PP ceramic diaphragm and embodiment 1 is made the full battery of 15Ah, shelve in 80 DEG C after being full of electricity and measure its capacity in 4 hours, charge again, test the capacity after its reply, its test result as shown in Figure 5, wherein: NW is ceramic diaphragm prepared by the present embodiment, PP is import PP ceramic diaphragm.
embodiment 2:
Select surface density 10 ~ 15g/m
2wet nonwoven fabrics as base material; In the ceramic solution of preparation, the mass percentage of each raw material is as follows: ceramic powder (Al (OH)
3): 22%; Carboxymethyl cellulose: 1%; Butadiene-styrene rubber: 10%; Deionized water: 67%.
Ceramic solution is coated in wet nonwoven fabrics substrate surface in the mode that nick is coated with, dry, namely obtain ceramic diaphragm.
embodiment 3:
Select surface density 15 ~ 25g/m
2wet nonwoven fabrics as base material; In the ceramic solution of preparation, the mass percentage of each raw material is as follows: ceramic powder (MgO and Al
2o
3, respectively account for the half of ceramic powder quality): 25%; Carboxymethyl cellulose: 3%; Butadiene-styrene rubber: 18%; Deionized water: 54%.
Base material is immersed in ceramic solution, take out dry, namely obtain ceramic diaphragm.
embodiment 4:
Select surface density 10 ~ 15g/m
2wet nonwoven fabrics as base material; In the ceramic solution of preparation, the mass percentage of each raw material is as follows: ceramic powder (TiO
2): 23%; Carboxymethyl cellulose: 2%; Butadiene-styrene rubber: 7%; Deionized water: 68%.
Ceramic solution is coated in wet nonwoven fabrics substrate surface (one side spraying) in the mode of spraying, takes out dry, namely obtain ceramic diaphragm.
test case:
The ceramic diaphragm choosing domestic PE ceramic diaphragm, import PP ceramic diaphragm and embodiment 1 carries out membrane properties contrast test, and test result is as shown in table 1.
The performance test data of the ceramic diaphragm of the domestic PE ceramic diaphragm of table 1, import PP ceramic diaphragm and embodiment 1
Note: the method for testing of thermal contraction test is as follows: square sample barrier film being die-cut into 100mm × 100mm, indicate MD and TD direction, measure the length of initial MD and TD, put it in the baking oven of 180 DEG C and toast 3h, the length in rear MD and the TD direction of test baking after taking out, calculates percent thermal shrinkage=[size before (size after the size-baking before baking)/baking] × 100%.
As shown in Table 1: the performance of the gas permeability of the ceramic diaphragm of embodiment 1, hot strength, the aspect such as elongation at break and percent thermal shrinkage is all better than domestic PE ceramic diaphragm and import PP ceramic diaphragm.
As shown in Figure 1: ceramic powder is evenly distributed on wet nonwoven fabrics.
As shown in Figure 2: the barrier film in (a) and (c) is from Fracture, and shrink very serious, the barrier film in (b) has slight contraction, and obvious contraction does not occur the barrier film in (d).
As shown in Figure 3: at 55 DEG C, ceramic diaphragm battery capacity conservation rate after carrying out 300 charge and discharge cycles of embodiment 1 is 84.63%, after carrying out 480 charge and discharge cycles, battery capacity conservation rate still has 78.86%, and import PP ceramic diaphragm battery capacity conservation rate after carrying out 300 charge and discharge cycles is only 69.02%.
As shown in Figure 4: under room temperature condition, ceramic diaphragm battery capacity conservation rate after carrying out 1450 charge and discharge cycles of embodiment 1 is 74.13%, and import ceramic diaphragm battery capacity conservation rate after carrying out 1000 charge and discharge cycles is only 46.72%.
As shown in Figure 5: the ceramic diaphragm of embodiment 1 is made the full battery of 15Ah, be full of electricity shelve 4h in 80 DEG C after, battery capacity residue reaches 89.1%, recharge, battery capacity response rate is 100%, and import ceramic diaphragm makes the full battery of 15Ah, be full of electricity shelve 4h in 80 DEG C after, battery capacity residue is only 76.5%, and recharge, battery capacity response rate is only 92.8%.
Above-described embodiment is the present invention's preferably execution mode; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from Spirit Essence of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. the wet nonwoven fabrics ceramic diaphragm of a lithium-ion-power cell is made up of base material and one side coating or coated on both sides, and it is characterized in that: described base material is wet nonwoven fabrics, described coating obtains by ceramic solution is coated to substrate surface.
2. ceramic diaphragm according to claim 1, is characterized in that: described wet nonwoven fabrics is surface density 6 ~ 10g/m
2, 10 ~ 15g/m
2, 15 ~ 25g/m
2nonwoven fabrics in one.
3. ceramic diaphragm according to claim 1, is characterized in that: the thickness of described base material is 12 ~ 15 μm.
4. ceramic diaphragm according to claim 1, is characterized in that: the thickness of described coating is 12 ~ 15 μm.
5. ceramic diaphragm according to claim 1, is characterized in that: described ceramic solution is made up of the raw material of following mass percentage: ceramic powder: 20% ~ 25%; Carboxymethyl cellulose: 1% ~ 3%; Butadiene-styrene rubber: 7% ~ 18%; Surplus is water.
6. ceramic diaphragm according to claim 5, is characterized in that: the particle diameter of described ceramic powder is 1 ~ 5 μm.
7. ceramic diaphragm according to claim 5, is characterized in that: described ceramic powder is SiO
2, Al
2o
3, Al (OH) 3, TiO
2, ZrO
2, at least one in MgO, SiC.
8. the preparation method of the ceramic diaphragm in claim 1 ~ 7 described in any one, it is characterized in that: comprise the following steps: first prepare ceramic solution, again ceramic solution is coated to matrix surface, namely obtains the wet nonwoven fabrics ceramic diaphragm of lithium-ion-power cell.
9. preparation method according to claim 8, is characterized in that: method ceramic solution being coated to matrix surface is at least one in nick coating, extrusion coated, dip-coating, spraying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610110894.9A CN105576178A (en) | 2016-02-29 | 2016-02-29 | Wet nonwoven fabric ceramic diaphragm of lithium ion power battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610110894.9A CN105576178A (en) | 2016-02-29 | 2016-02-29 | Wet nonwoven fabric ceramic diaphragm of lithium ion power battery and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN105576178A true CN105576178A (en) | 2016-05-11 |
Family
ID=55886081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610110894.9A Pending CN105576178A (en) | 2016-02-29 | 2016-02-29 | Wet nonwoven fabric ceramic diaphragm of lithium ion power battery and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932325A (en) * | 2016-07-18 | 2016-09-07 | 上海空间电源研究所 | Long-storage life lithium ion storage battery |
| CN108807787A (en) * | 2018-05-02 | 2018-11-13 | 名添科技（深圳）有限公司 | A kind of preparation method of lithium battery power diaphragm |
| CN110915023A (en) * | 2018-04-18 | 2020-03-24 | 株式会社Lg化学 | Flame retardant separator having asymmetric structure for secondary battery |
| WO2024131601A1 (en) * | 2022-12-20 | 2024-06-27 | 宁德时代新能源科技股份有限公司 | Separator film, battery and electrical apparatus |
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| US4812375A (en) * | 1988-06-27 | 1989-03-14 | The United States Of America As Represented By The Secretary Of The Army | Separator for lithium batteries and lithium batteries including the separator |
| EP0959510A2 (en) * | 1998-05-22 | 1999-11-24 | Teijin Limited | Electrolytic-solution-supporting polymer film and secondary battery |
| CN103026530A (en) * | 2010-08-11 | 2013-04-03 | 科德宝两合公司 | Separator with increased puncture resistance |
| CN103199209A (en) * | 2013-04-01 | 2013-07-10 | 中国海诚工程科技股份有限公司 | Non-woven ceramic membrane with excellent closed-pore performance for lithium ion battery and technology |
| CN103545472A (en) * | 2012-07-17 | 2014-01-29 | 比亚迪股份有限公司 | Composite diaphragm for lithium battery as well as preparation method thereof and lithium battery including composite diaphragm |
| CN104303335A (en) * | 2012-05-23 | 2015-01-21 | 三菱制纸株式会社 | Lithium-ion battery separator |
| CN104466062A (en) * | 2014-12-10 | 2015-03-25 | 厦门大学 | Boron-containing ceramic separator as well as preparation method and application thereof |
| CN105273444A (en) * | 2014-07-23 | 2016-01-27 | 乐凯胶片股份有限公司 | Slurry composition and lithium ion battery diaphragm containing same |
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2016
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| US4812375A (en) * | 1988-06-27 | 1989-03-14 | The United States Of America As Represented By The Secretary Of The Army | Separator for lithium batteries and lithium batteries including the separator |
| EP0959510A2 (en) * | 1998-05-22 | 1999-11-24 | Teijin Limited | Electrolytic-solution-supporting polymer film and secondary battery |
| CN103026530A (en) * | 2010-08-11 | 2013-04-03 | 科德宝两合公司 | Separator with increased puncture resistance |
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| CN105273444A (en) * | 2014-07-23 | 2016-01-27 | 乐凯胶片股份有限公司 | Slurry composition and lithium ion battery diaphragm containing same |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932325A (en) * | 2016-07-18 | 2016-09-07 | 上海空间电源研究所 | Long-storage life lithium ion storage battery |
| CN110915023A (en) * | 2018-04-18 | 2020-03-24 | 株式会社Lg化学 | Flame retardant separator having asymmetric structure for secondary battery |
| CN110915023B (en) * | 2018-04-18 | 2022-07-08 | 株式会社Lg化学 | Flame retardant separator having asymmetric structure for secondary battery |
| CN108807787A (en) * | 2018-05-02 | 2018-11-13 | 名添科技（深圳）有限公司 | A kind of preparation method of lithium battery power diaphragm |
| WO2024131601A1 (en) * | 2022-12-20 | 2024-06-27 | 宁德时代新能源科技股份有限公司 | Separator film, battery and electrical apparatus |
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Application publication date: 20160511 |