CN109686903A - A kind of active material modification diaphragm and preparation method thereof - Google Patents
A kind of active material modification diaphragm and preparation method thereof Download PDFInfo
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- CN109686903A CN109686903A CN201811500349.6A CN201811500349A CN109686903A CN 109686903 A CN109686903 A CN 109686903A CN 201811500349 A CN201811500349 A CN 201811500349A CN 109686903 A CN109686903 A CN 109686903A
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- film
- active material
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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
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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
-
- 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 Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
本发明公开了一种活性材料修饰隔膜及其制备方法，该隔膜包括：具有绝缘及支撑作用的基膜层、可同锂枝晶反应的活性物质层。所述基膜为聚乙烯膜、聚丙烯膜、聚偏氟乙烯膜、聚偏氟乙烯‑六氟丙烯膜、聚酰亚胺膜、聚酰胺膜、聚四氟乙烯膜、聚炳烯酸酯类膜、聚氯乙烯膜、聚环氧乙烯膜、玻璃纤维膜、纤维素膜、无纺布膜中的一种或多种复合膜。所述活性物质层的制备方法是将活性物质同粘结剂制成混合浆料，然后沉积到基膜上。所述沉积方法是刮涂、转移涂、喷涂、磁控溅射、粒子束溅射、原子层沉积、电子束蒸镀、脉冲激光沉积、气相沉积。所述活性物质层至少沉积于隔膜一侧。
The invention discloses an active material modified diaphragm and a preparation method thereof. The diaphragm comprises a base film layer with insulating and supporting functions, and an active material layer capable of reacting with lithium dendrites. The base film is polyethylene film, polypropylene film, polyvinylidene fluoride film, polyvinylidene fluoride-hexafluoropropylene film, polyimide film, polyamide film, polytetrafluoroethylene film, polyacrylic acid ester One or more composite films selected from quasi film, polyvinyl chloride film, polyethylene oxide film, glass fiber film, cellulose film and non-woven film. The preparation method of the active material layer is that the active material and the binder are made into a mixed slurry, and then deposited on the base film. The deposition methods are blade coating, transfer coating, spray coating, magnetron sputtering, particle beam sputtering, atomic layer deposition, electron beam evaporation, pulsed laser deposition, and vapor deposition. The active material layer is deposited on at least one side of the diaphragm.
Description
Technical field
The invention belongs to electrochemical energy storage technical fields, and in particular, to be used for lithium ion battery or lithium metal to a kind of
New types of diaphragm of battery and preparation method thereof.
Background technique
With increasingly serious, need of the people for clean and effective and renewable energy of world today's energy and environment problem
It asks and is continuously increased, the Efficient Conversion of energy and storage are also of increasing concern.High-energy density and environmental-friendly lithium-ion electric
Pond and lithium metal battery become important research direction in recent years.However no matter lithium ion battery or lithium metal battery all exist
Li dendrite problem, wherein lithium metal battery is even more serious.The Li dendrite that cathode generates in cyclic process, which pierces through diaphragm, leads to battery
Short circuit influences battery life, forms security risk.
Inhibit the method for Li dendrite to have from diaphragm angle at present: diaphragm, enhancing diaphragm base are filled or coated using compound
Material intensity, improvement membrane configuration intensity etc..The above method is increased by enhancing the mechanical strength of diaphragm itself
Strong diaphragm is limited to the inhibiting effect of Li dendrite to the resistance of Li dendrite.Application for a patent for invention 201710493913.5 proposes
Active interlayer is introduced in diaphragm, so that active interlayer is reacted with metal Li dendrite, to convert inertia for Li dendrite
The method of insulation product.
This method can farthest alleviate Li dendrite problem, but construct three-layer membrane, and preparation method is complex, work
Skill is cumbersome.The present invention further simplifies the preparation method of active interlayer diaphragm in application for a patent for invention 201710493913.5,
And diaphragm is made to increase new function in original effect for inhibiting Li dendrite.
Summary of the invention
In application for a patent for invention 201710493913.5, the diaphragm comprising active interlayer include base membrane layer, active interlayer,
Another layer insulating three parts, activity interlayer modification diaphragm proposed by the present invention only includes base membrane layer and active layer, the activity
For layer when contacting in the battery with positive or negative pole, active layer surface, which reacts, generates insulating layer, in active layer not with anode or
Cathode contact part, which will not participate in reaction, still can be used as active interlayer use.In addition, when active layer and anode contact, in battery head
In secondary discharge process, contact portion can be used as anode and participate in electric discharge, increase the discharge capacity for the first time of battery；Active layer and negative
When pole contacts, contact portion reacts with lithium metal, can promote lithium metal activation, forms new SEI film in metallic lithium surface.
A kind of active material modifies diaphragm, which includes: base membrane layer with insulation and supporting role, can same Li dendrite
The active material layer of reaction.The basement membrane is polyethylene film, polypropylene screen, polyvinylidene fluoride film, Kynoar-hexafluoropropene
Film, polyimide film, PA membrane, polytetrafluoroethylene film, polypropylene esters of gallic acid film, polychloroethylene film, Pluronic F-127 film, glass
One of glass tunica fibrosa, cellulose membrane, non-woven membrane or a variety of composite membranes.The active material layer is by active material and bonding
Agent composition, activity substance content are 10~100%.
Further, the active material is I2、S、V2O5、MoO3、MnO2、Bi2O3、Bi2Pb2O5, fluorocarbons, CuCl2、
CuF2、CuO、CuS、FeS、FeS2、Ni2S2、AgCl、Ag2CrO4One of or it is a variety of.
Further, the binder is La132, La133, polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, carboxymethyl
Sodium cellulosate, sodium alginate.
Another technical solution of the invention is, the preparation method of above-mentioned active material modification diaphragm is provided, by active matter
Mixed slurry is made with binder in matter, is then deposited on basement membrane.The deposition method is blade coating, transfer is applied, sprayed, magnetic control splashes
It penetrates, particle beam sputtering, atomic layer deposition, electron beam evaporation plating, pulse laser deposition, vapor deposition.
Further, the active material layer is least deposited in diaphragm side.
Detailed description of the invention
Fig. 1 is the schematic cross-section of diaphragm of the present invention.
Fig. 2 is the SEM figure of diaphragm coating surface prepared by embodiment 1.
Fig. 3 is the discharge curve for the first time of battery prepared by embodiment 1 and comparative example 1.
Specific embodiment
Below in conjunction with attached drawing and the embodiment technical solution that the present invention will be described in detail.
As shown in Figure 1, for the diaphragm of the present invention comprising active interlayer, which includes basement membrane 2, active interlayer 1.
Embodiment 1
It weighs 0.1g La132 to be added in 30g deionized water, be completely dissolved with magnetic stirrer to La133；It weighs
1g fluorocarbons is added in La133 solution, and stirring 2h obtains mixed slurry.By active slurry blade coating on polyethylene diagrams, it is put into
60 DEG C of oven dryings.
Using lithium metal as cathode, sulphur carbon composite is anode, and above-mentioned diaphragm coating assembles flexible-packed battery to anode.Electricity
Pond vacuumizes after standing 48 hours.Electric performance test is carried out to battery with the charge-discharge magnification of 0.05C.
Fig. 2 is the SEM figure of diaphragm coating surface prepared by embodiment 1.Membrane surface uniform fold is fluorinated carbon particle.
Comparative example 1
Using lithium band as cathode, sulfur-bearing positive electrode is anode, assembles flexible-packed battery using uncoated polyethylene diagrams.
Battery standing vacuumizes after 48 hours.Electric performance test is carried out to battery with the charge-discharge magnification of 0.05C.
Fig. 3 is the discharge curve for the first time of battery prepared by embodiment 1 and comparative example 1.As seen from the figure prepared by embodiment 1
Battery has increased fluorocarbons discharge platform newly on elemental sulfur conventional discharge platform base in discharge curve for the first time, and battery discharges for the first time
Capacity is 468mAh, and battery cycle life is up to 138 times；Comparative example 1 prepares battery, and discharge curve is that elemental sulfur electric discharge is bent for the first time
Line, discharge capacity is 401mAh to battery for the first time, and battery cycle life is 45 times.
Embodiment 2
It weighs 0.01g PVDF to be added in 30g NMP, be completely dissolved with magnetic stirrer to PVDF；Weigh 0.5g
MnO2Material is added in PVDF solution, and stirring 6h obtains mixed slurry.Active slurry transfer is coated on glass fibre membrane, is put into
100 DEG C of oven dryings.
Using lithium metal as cathode, carbon sulphur composite material is anode, and above-mentioned diaphragm coating assembles flexible-packed battery to cathode.
Battery standing vacuumizes after 48 hours.Electric performance test is carried out to battery with the charge-discharge magnification of 0.1C.Battery discharges appearance for the first time
Amount is 410mAh, and cycle life is 155 times.
It is discussed in detail although the contents of the present invention have passed through above preferred embodiment, but it should be appreciated that above-mentioned
Description is not considered as limitation of the present invention.After those skilled in the art have read above content, for of the invention
A variety of modifications and substitutions all will be apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (5)
1. a kind of active material modifies diaphragm characterized by comprising have insulation and supporting role base membrane layer, can same lithium
The active material layer of dendrite reaction；
The basement membrane is polyethylene film, polypropylene screen, polyvinylidene fluoride film, Kynoar-hexafluoropropene film, polyimides
Film, PA membrane, polytetrafluoroethylene film, polypropylene esters of gallic acid film, polychloroethylene film, Pluronic F-127 film, glass fibre membrane, fibre
Tie up one of plain film, non-woven membrane or a variety of composite membranes；
The active material layer is made of active material and binder, and activity substance content is 10~100%.
2. a kind of active material as described in claim 1 modifies diaphragm, which is characterized in that the active material is I2、S、
V2O5、MoO3、MnO2、Bi2O3、Bi2Pb2O5, fluorocarbons, CuCl2、CuF2、CuO、CuS、FeS、FeS2、Ni2S2、AgCl、
Ag2CrO4One of or it is a variety of.
3. a kind of active material as described in claim 1 modifies diaphragm, which is characterized in that the binder be La132,
La133, polytetrafluoroethylene (PTFE), Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, sodium alginate.
4. a kind of preparation method of active material modification diaphragm as described in claim 1, which is characterized in that the active material
Layer is that mixed slurry is made with binder in active material, is then deposited on basement membrane；
The method of the deposition is blade coating, transfer painting, spraying, magnetron sputtering, particle beam sputtering, atomic layer deposition, electron beam steaming
Plating, pulse laser deposition, vapor deposition.
5. a kind of preparation method of active material modification diaphragm as claimed in claim 4, which is characterized in that the active material
Layer is least deposited in diaphragm side.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811500349.6A CN109686903A (en) | 2018-12-07 | 2018-12-07 | A kind of active material modification diaphragm and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811500349.6A CN109686903A (en) | 2018-12-07 | 2018-12-07 | A kind of active material modification diaphragm and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN109686903A true CN109686903A (en) | 2019-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201811500349.6A Pending CN109686903A (en) | 2018-12-07 | 2018-12-07 | A kind of active material modification diaphragm and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114709554A (en) * | 2022-03-31 | 2022-07-05 | 西北工业大学 | Ion battery functionalized textile cotton cloth diaphragm and preparation method and application thereof |
| CN115133222A (en) * | 2022-06-06 | 2022-09-30 | 西北工业大学 | Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, preparation method and lithium metal battery applying diaphragm |
| CN118281487A (en) * | 2024-05-31 | 2024-07-02 | 江苏正力新能电池技术有限公司 | Lithium ion battery |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477491A (en) * | 2011-02-15 | 2013-12-25 | Lg化学株式会社 | Separator, preparation method thereof, and electrochemical device comprising same |
| US20140205883A1 (en) * | 2012-03-28 | 2014-07-24 | Sharp Laboratories Of America, Inc. | Reactive separator for a metal-ion battery |
| CN105140449A (en) * | 2015-08-14 | 2015-12-09 | 中国人民解放军63971部队 | Method for protecting anode of lithium sulfur battery |
| CN107316967A (en) * | 2017-06-26 | 2017-11-03 | 上海空间电源研究所 | A kind of barrier film, preparation method and the usage for including active interlayer |
-
2018
- 2018-12-07 CN CN201811500349.6A patent/CN109686903A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477491A (en) * | 2011-02-15 | 2013-12-25 | Lg化学株式会社 | Separator, preparation method thereof, and electrochemical device comprising same |
| US20140205883A1 (en) * | 2012-03-28 | 2014-07-24 | Sharp Laboratories Of America, Inc. | Reactive separator for a metal-ion battery |
| CN105140449A (en) * | 2015-08-14 | 2015-12-09 | 中国人民解放军63971部队 | Method for protecting anode of lithium sulfur battery |
| CN107316967A (en) * | 2017-06-26 | 2017-11-03 | 上海空间电源研究所 | A kind of barrier film, preparation method and the usage for including active interlayer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114709554A (en) * | 2022-03-31 | 2022-07-05 | 西北工业大学 | Ion battery functionalized textile cotton cloth diaphragm and preparation method and application thereof |
| CN114709554B (en) * | 2022-03-31 | 2023-03-24 | 西北工业大学 | Ion battery functionalized textile cotton cloth diaphragm and preparation method and application thereof |
| CN115133222A (en) * | 2022-06-06 | 2022-09-30 | 西北工业大学 | Double-coating diaphragm capable of simultaneously inhibiting lithium dendrite and transition metal dissolution, preparation method and lithium metal battery applying diaphragm |
| CN118281487A (en) * | 2024-05-31 | 2024-07-02 | 江苏正力新能电池技术有限公司 | Lithium ion battery |
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Application publication date: 20190426 |