CN110783512B - Soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for lithium ion battery and preparation method thereof - Google Patents
Soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for lithium ion battery and preparation method thereof Download PDFInfo
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- 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
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- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
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Abstract
The invention relates to a soluble type lithium bifluoride sulfimide/magnesium silicate lithium coating diaphragm for a lithium battery and a preparation method thereof, wherein the diaphragm comprises a base film and a coating coated on one side of the base film, the one side of the base film is the surface of the diaphragm facing to one side of a negative electrode, and the coating comprises lithium bifluoride sulfimide, magnesium silicate lithium, polymethyl methacrylate and a solvent; the preparation method specifically comprises the steps of firstly preparing the lithium magnesium silicate/polymethyl methacrylate composite particles, then mixing the particles with the lithium bis (fluorosulfonyl) imide, dissolving the mixture in a solvent to obtain a stable dispersion liquid, finally spraying the prepared stable dispersion liquid on the surface of the diaphragm base material on one side, which faces to the negative electrode, during winding, and drying. The soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coated diaphragm for the lithium battery has the characteristics of reducing the deformation of a roll core and increasing the transference number of lithium ions of electrolyte, and the preparation method of the diaphragm has the advantages of easily available raw materials, simplicity and convenience in operation and easiness in realization of industrial operation.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery diaphragms, and particularly relates to a soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for a lithium ion battery and a preparation method thereof.
Background
In the using process of the lithium ion battery, the thickness of the electrode pole piece can be changed to a certain extent, in particular to a graphite negative electrode. According to the existing data, after the lithium battery is stored and circulated at high temperature, the expansion rate of the positive electrode is only 4 percent, and the expansion rate of the negative electrode is more than 20 percent. The root cause of the deformation of the winding core and the pole piece caused by the increase of the thickness of the negative pole piece of the lithium battery is graphite, and LiCx (LiC) is formed when the negative pole graphite is embedded with lithium24、LiC12And LiC6Etc.), lattice spacing changes, resulting in volume expansion of graphite particlesThe change further releases the internal stress of the negative electrode to generate irreversible expansion, and the expansion is mainly related to the particle size, the adhesive and the structure of the pole piece.
The expansion of the negative electrode after lithium intercalation occurs after the winding of the winding core is finished, at the moment, the diaphragm and the positive electrode are fixed, the expansion of the negative electrode can form larger internal stress of the winding core, the winding core and the pole piece are deformed, a cavity is formed between the negative electrode and the diaphragm, lithium deintercalation is not uniform, a negative electrode coating and particles form microcracks, a Solid Electrolyte Interface (SEI) film is cracked and recombined, electrolyte is consumed, and the cycle performance is poor.
How to avoid the deformation of the winding core and ensure good diaphragm and pole piece interfaces becomes an urgent task for the development of lithium ion batteries. Due to the continuous lithium deintercalation reaction inside lithium batteries, the corresponding technical development also considers the influence of side reactions on the battery performance.
Aiming at the problem of the deformation of the winding core, the PVDF (polyvinylidene fluoride) coating diaphragm is widely adopted at present, the PVDF coating diaphragm or the two surfaces of the ceramic diaphragm are coated, the PVDF glue layer on the surface of the diaphragm can tightly attach the diaphragm with the anode and the cathode together when the winding core is hot-pressed, the deformation of the winding core under the action of internal stress is inhibited, and the internal stress of the winding core caused by irreversible expansion after lithium is removed and embedded from the cathode is not fundamentally eliminated or reduced. The PVDF coating diaphragm needs to accurately regulate and control the hot-pressing parameters, so that the situation that the glue layer blocks infiltration between a negative electrode and electrolyte to cause lithium precipitation during first charging is avoided, and the PVDF glue layer gradually swells along with the prolonging of the time of soaking the electrolyte, and the adhesion force is gradually weakened or even loses efficacy.
Chinese patent with publication number CN106784532A discloses a preparation method of a water-based PVDF and a copolymer composite coating membrane thereof, the aqueous PVDF and the copolymer composite coating diaphragm thereof are obtained by mixing PVDF, the copolymer thereof and ceramics into slurry according to a certain proportion, coating the slurry on one side or two sides of a basal membrane according to a certain coating mode, drying the slurry in a three-stage oven at the temperature of 40-90 ℃, thereby improving the swelling ratio of the diaphragm in electrolyte, the rate discharge performance and the cycle performance of the lithium ion battery, but the patent adopts the composite coating of the aqueous PVDF and the copolymer thereof on the diaphragm, the problem of deformation of a winding core in the use process of the lithium ion battery is not fundamentally solved, the adhesion force of a diaphragm coating is gradually weakened or even loses efficacy along with the increase of the charging and discharging times of the battery, the winding core and a pole piece in the battery are gradually deformed, and the multiplying power discharge performance and the cycle performance of the lithium ion battery are further influenced; in addition, the components of the coated separator in this patent include PVDF and its copolymers, ceramics, dispersants, and ionic water, and the promotion of the components thereof to other electrical properties of the battery is not sufficiently considered.
Disclosure of Invention
The invention aims to provide a soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for a lithium ion battery and a preparation method thereof, wherein the diaphragm has the characteristics of reducing the deformation of a winding core and increasing the transference number of lithium ions of an electrolyte, the problem of internal stress of the winding core caused by irreversible expansion after lithium is embedded in a negative electrode is fundamentally solved or reduced, and the preparation method of the diaphragm has the advantages of easily obtained raw materials, simplicity and convenience in operation and easiness in realizing industrial operation.
The technical scheme adopted by the invention for solving the problems is as follows: a soluble type lithium bis (fluorosulfonyl) imide/magnesium lithium silicate coating diaphragm for a lithium battery comprises a base film and a coating coated on one side of the base film, wherein the one side of the base film is the surface of the diaphragm facing to one side of a negative electrode, and the coating comprises lithium bis (fluorosulfonyl) imide, magnesium lithium silicate, polymethyl methacrylate and a solvent.
Preferably, the base film is a polyethylene base film, a polypropylene base film, a non-woven fabric diaphragm base film, or a cellulose base film.
Preferably, the magnesium lithium silicate comprises all montmorillonite products with silicon, oxygen, magnesium, sodium and lithium as main elements and surface treatment or ion replacement products thereof, and the amount of the magnesium lithium silicate is 0.1-10% of the weight of the solvent.
Preferably, the lithium bis (fluorosulfonyl) imide is battery-grade lithium bis (fluorosulfonyl) imide, and the amount of the lithium bis (fluorosulfonyl) imide is 0.1-10% of the weight of the solvent.
Preferably, the amount of the polymethyl methacrylate is 0.1 to 10% by weight of the solvent.
Preferably, the solvent is one or more of ethylene carbonate, ethyl acetate and propylene carbonate.
The invention also aims to provide a preparation method of the soluble lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for the lithium battery, which comprises the following steps:
(1) preparing the magnesium lithium silicate/polymethyl methacrylate composite particle emulsion through in-situ emulsion polymerization, and preparing the magnesium lithium silicate/polymethyl methacrylate composite particles through spray drying.
(2) Dissolving the magnesium lithium silicate/polymethyl methacrylate composite particles obtained in the step (1) and lithium bis (fluorosulfonyl) imide in a solvent, and then adding the solution into a stirrer for vacuumizing and stirring.
(3) And (3) spraying the stable dispersion liquid stirred in the step (2) on the surface of the diaphragm base material facing the negative electrode side during winding, drying, and repeating the spraying and drying steps for 2-5 times to form an electrolyte-soluble coating with the thickness of about 5-10 mu m, wherein the thickness of the coating is determined by the irreversible rebound thickness of the negative electrode after winding by a winding core.
Preferably, the drying temperature in step (3) is 60 ℃.
The diaphragm prepared by the invention is applied to a lithium battery, as shown in figure 1, when winding is finished, the dissolvable diaphragm coating in the winding core occupies a space with the thickness of about 5-10 mu m; after the electrolyte is injected, the negative electrode begins to expand after being soaked in the electrolyte, the soluble diaphragm coating is gradually dissolved by the electrolyte, and meanwhile, the magnesium lithium silicate, the polymethyl methacrylate and the lithium bis (fluorosulfonyl) imide dissolved in the electrolyte begin to diffuse; after the lithium battery is charged and discharged, the negative electrode is completely expanded and stable, and meanwhile, the expansion and contraction of the negative electrode can generate the extrusion and absorption effects of electrolyte in the charging and discharging process, so that the dissolution of the dissolvable diaphragm coating and the diffusion of the dissolvable diaphragm coating in the whole roll core range are further promoted. When the soluble diaphragm coating is completely dissolved, the winding core can absorb the expansion of about 5-10 mu m of the negative electrode without generating obvious internal stress, thereby fundamentally lightening the deformation of the winding core and the pole piece.
Compared with the prior art, the invention has the advantages that:
(1) the diaphragm coating comprises the lithium bifluorosulfonate and the lithium magnesium silicate, wherein the lithium bifluorosulfonate can effectively reduce the impedance generated by an SEI film formed on a negative electrode and reduce the capacity loss of a lithium battery in the storage process, so that the capacity and the electrochemical performance of the battery are improved, the lithium ion migration number of an electrolyte can be improved, and the polarization of the battery is reduced; the magnesium lithium silicate is a nanosheet single-ion conductor which is low in price and environment-friendly, and can promote the dissociation of electrolyte salt and improve the transference number of electrolyte lithium ions; polymethyl methacrylate is readily soluble in ethyl acetate, one of the main components of the electrolyte.
(2) The diaphragm coating can be dissolved in electrolyte, and a space for absorbing and expanding is created for the negative electrode through the dissolution of the diaphragm coating after the winding of the winding core is finished, so that the internal stress of the winding core generated by the expansion of the negative electrode is greatly reduced, the winding core has a smoother diaphragm pole piece interface, and the performance and the service life of the battery are improved.
(3) The selected coating components fully consider the influence on the electrolyte and the electrical property, and when the soluble diaphragm coating is dissolved into the electrolyte, all the components can improve the lithium ion migration number of the electrolyte to a certain extent, so that the polarization of the battery in the charging and discharging process can be obviously reduced, the SEI film impedance is reduced, and the direct current internal resistance of the battery is obviously reduced.
(4) The soluble diaphragm coating has the advantages of simple preparation method, easily obtained raw materials, low cost and easy realization of industrial operation.
Drawings
Fig. 1 is a schematic view of a separator of the present invention in a lithium battery;
wherein, 1, a partial schematic diagram of a winding core before liquid injection; 2. the partial schematic diagram of the liquid-injected winding core; 3. partial schematic diagram of the winding core after charging and discharging;
1.1, a coiled core anode before liquid injection; 1.2, winding core cathode before liquid injection; 1.3, winding core diaphragm basement membrane before liquid injection; 1.4, coating a core diaphragm before liquid injection;
2.1, winding core anode after liquid injection; 2.2, a coiled core cathode after liquid injection; 2.3, winding core diaphragm basement membrane after liquid injection; 2.4 coating the diaphragm of the winding core after liquid injection;
3.1, a coiled core anode after charging and discharging; 3.2, a coiled core cathode after charging and discharging; 3.3, winding core diaphragm basement membrane after charging and discharging;
fig. 2 is a diagram of direct current internal resistance measured after a battery cell is manufactured by using the separator in embodiment 1 of the present invention;
fig. 3 is a diagram of direct current internal resistance measured after a battery cell is manufactured from the separator in embodiment 2 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
A soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coated diaphragm for a lithium ion battery is characterized in that a base film is made of polyethylene, a ceramic coating is coated on one side, facing a positive electrode, of the base film, and a coating comprising lithium magnesium silicate, battery-grade high-purity lithium bis (fluorosulfonyl) imide and polymethyl methacrylate is coated on the surface, facing a negative electrode, of the base film.
A preparation method of a soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for a lithium ion battery comprises the following steps:
(1) mixing magnesium lithium silicate and methyl methacrylate according to the weight ratio of 1:10, performing ultrasonic oscillation, preparing magnesium lithium silicate/polymethyl methacrylate composite particle emulsion by adopting an in-situ emulsion polymerization method, and preparing the composite emulsion into magnesium lithium silicate/polymethyl methacrylate composite particles by adopting a spray drying method.
(2) 8g of magnesium lithium silicate/polymethyl methacrylate composite particles and 4g of lithium bis (fluorosulfonyl) imide were dissolved in 200g of an ethyl acetate/ethylene carbonate mixed solution at a weight ratio of 8:2, and mixed under vacuum with stirring parameters of a revolution speed of 15rpm and a dispersion speed of 1500rpm to prepare a stable dispersion.
(3) And spraying the prepared stable dispersion liquid on the surface of the diaphragm base material on the side opposite to the negative electrode in winding, drying at the drying temperature of 60 ℃, and repeating the spraying and drying steps for 3 times to form an electrolyte-soluble coating with the thickness of about 10 mu m.
Example 2
A soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coated diaphragm for lithium ion battery is prepared as coating base film on positive electrode side of polypropylene, coating ceramic coating on surface of base film on negative electrode side, coating layer containing lithium magnesium silicate, battery-grade high-purity lithium bis (fluorosulfonyl) imide and polymethyl methacrylate on surface of base film.
A preparation method of a soluble lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for a lithium battery comprises the following steps:
(1) mixing magnesium lithium silicate and methyl methacrylate according to the weight ratio of 1:20, performing ultrasonic oscillation, preparing magnesium lithium silicate/polymethyl methacrylate composite particle emulsion by adopting an in-situ emulsion polymerization method, and preparing the composite emulsion into magnesium lithium silicate/polymethyl methacrylate composite particles by adopting a spray drying method.
(2) 10g of magnesium lithium silicate/polymethyl methacrylate composite particles and 20g of lithium bis (fluorosulfonyl) imide were dissolved in 150g of a mixed solution of ethyl acetate/ethylene carbonate/propylene carbonate in a weight ratio of 8:1:1, and the mixture was mixed under vacuum at a revolution speed of 15rpm and a dispersion speed of 1500rpm to prepare a stable dispersion.
(3) And spraying the prepared stable dispersion liquid on the surface of the diaphragm base material on the side opposite to the negative electrode in winding, drying at the drying temperature of 60 ℃, and repeating the spraying and drying steps for 3 times to form an electrolyte-soluble coating with the thickness of about 8 mu m.
In order to verify the effect of the invention, after the separator obtained in the embodiment 1 and the embodiment 2 is manufactured into the 1# cell and the 2# cell, the direct current internal resistance is tested, and the separator is fully disassembled after circulating for a certain number of times, and the core state and the pole piece interface are observed.
1. Direct current resistance test
In fig. 2, a broken line 1 is the discharging direct-current internal resistance of the 1# battery cell 10% -90% SOC, a broken line 2 is the charging direct-current internal resistance of the 1# battery cell 10% -90% SOC, a broken line 3 is the discharging direct-current internal resistance of the 2# battery cell 10% -90% SOC, and a broken line 4 is the charging direct-current internal resistance of the 2# battery cell 10% -90% SOC. As can be seen from fig. 2 and 3, the charging and discharging direct current internal resistances of the battery cells are both very low, and the discharging direct current internal resistance of the 1# battery cell with 50% SOC is 0.280m Ω, which is only higher than the alternating current impedance of the battery cell by about 0.02m Ω; the discharging direct current internal resistance of the 2# battery cell with the SOC of 50% is 0.276m omega, and is only about 0.017m omega higher than the alternating current impedance of the battery cell. The charging direct-current internal resistances of the 1# cell and the 2# cell are kept stable in the whole SOC variation range, the maximum value of the charging direct-current internal resistance of the 1# cell is 0.307m omega, the maximum value of the charging direct-current internal resistance of the 2# cell is 0.304m omega, the charging direct-current internal resistance is only 0.044m omega higher than the alternating-current impedance, and the direct-current internal resistance is not obviously higher than the alternating-current impedance due to internal polarization in a 4C mixed pulse power test of the 1# cell and the 2# cell.
2. Interface between roll core state and diaphragm sheet
The separator obtained in the embodiments 1 and 2 is manufactured into the battery cell 1 and the battery cell 2, and the battery cell 1 and the battery cell 2 both circulate 50 times and then observe the roll state and the interface of the separator pole piece, and the result is: no matter roll up core outer lane or roll up core inner circle and all keep good negative pole diaphragm interface, the negative pole surface color is homogeneous golden yellow.
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (8)
1. A lithium battery is with soluble type lithium bifluorosulfonimide/lithium magnesium silicate coating diaphragm which characterized in that: the lithium battery diaphragm comprises a base film and a coating coated on one side of the base film, wherein the one side of the base film is the surface of the diaphragm facing to one side of a negative electrode, and the coating comprises lithium bis (fluorosulfonyl) imide, lithium magnesium silicate, polymethyl methacrylate and a solvent;
the preparation method of the soluble lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coated diaphragm for the lithium battery comprises the following steps:
(1) preparing magnesium lithium silicate/polymethyl methacrylate composite particle emulsion through in-situ emulsion polymerization, and preparing magnesium lithium silicate/polymethyl methacrylate composite particles through spray drying;
(2) dissolving the magnesium lithium silicate/polymethyl methacrylate composite particles obtained in the step (1) and lithium bis (fluorosulfonyl) imide in a solvent, and then adding the solution into a stirrer for vacuumizing and stirring;
(3) and (3) spraying the stable dispersion liquid stirred in the step (2) on the surface of the diaphragm base material on the side opposite to the negative electrode in winding, drying, and repeating the spraying and drying steps for 2-5 times to form an electrolyte-soluble coating with the thickness of 5-10 mu m, wherein the thickness of the coating is determined by the irreversible rebound thickness of the negative electrode after winding by a winding core.
2. The lithium battery soluble lithium bis-fluorosulfonylimide/lithium magnesium silicate coated separator of claim 1, wherein: the base film is a polyethylene base film, a polypropylene base film, a non-woven fabric diaphragm base film and a cellulose base film.
3. The lithium battery soluble lithium bis-fluorosulfonylimide/lithium magnesium silicate coated separator of claim 1, wherein: the magnesium lithium silicate comprises montmorillonite products which take silicon, oxygen, magnesium, sodium and lithium as main elements and surface treatment or ion replacement products thereof, and the dosage of the magnesium lithium silicate is 0.1-10% of the weight of the solvent.
4. The lithium battery soluble lithium bis-fluorosulfonylimide/lithium magnesium silicate coated separator of claim 1, wherein: the lithium bis (fluorosulfonyl) imide is battery-grade lithium bis (fluorosulfonyl) imide, and the amount of the lithium bis (fluorosulfonyl) imide is 0.1-10% of the weight of the solvent.
5. The lithium battery soluble lithium bis-fluorosulfonylimide/lithium magnesium silicate coated separator of claim 1, wherein: the amount of the polymethyl methacrylate is 0.1-10% of the weight of the solvent.
6. The lithium battery soluble lithium bis-fluorosulfonylimide/lithium magnesium silicate coated separator of claim 1, wherein: the solvent is one or more of ethylene carbonate, ethyl acetate and propylene carbonate.
7. A method of preparing a soluble lithium bis-fluorosulfonylimide/lithium magnesium silicate coated separator for lithium batteries as claimed in claim 1 comprising the steps of:
(1) preparing magnesium lithium silicate/polymethyl methacrylate composite particle emulsion through in-situ emulsion polymerization, and preparing magnesium lithium silicate/polymethyl methacrylate composite particles through spray drying;
(2) dissolving the magnesium lithium silicate/polymethyl methacrylate composite particles obtained in the step (1) and lithium bis (fluorosulfonyl) imide in a solvent, and then adding the solution into a stirrer for vacuumizing and stirring;
(3) and (3) spraying the stable dispersion liquid stirred in the step (2) on the surface of the diaphragm base material on the side opposite to the negative electrode in winding, drying, and repeating the spraying and drying steps for 2-5 times to form an electrolyte-soluble coating with the thickness of 5-10 mu m, wherein the thickness of the coating is determined by the irreversible rebound thickness of the negative electrode after winding by a winding core.
8. The method of preparing a lithium battery soluble lithium bis fluorosulfonylimide/lithium magnesium silicate coated separator according to claim 7, wherein: the drying temperature in the step (3) is 60 ℃.
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| CN201910985702.2A CN110783512B (en) | 2019-10-17 | 2019-10-17 | Soluble type lithium bis (fluorosulfonyl) imide/lithium magnesium silicate coating diaphragm for lithium ion battery and preparation method thereof |
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| EP4199232A1 (en) * | 2020-08-14 | 2023-06-21 | Ubatt Inc. | Separator for electrochemical element |
| CN114284642A (en) * | 2021-11-24 | 2022-04-05 | 荣盛盟固利新能源科技股份有限公司 | Multilayer coating diaphragm and polymer battery prepared from same |
| CN114464951A (en) * | 2022-01-26 | 2022-05-10 | 珠海冠宇电池股份有限公司 | Diaphragm containing fulcrum and battery containing diaphragm |
| CN115241604A (en) * | 2022-07-08 | 2022-10-25 | 珠海冠宇电池股份有限公司 | Separator and battery |
| CN117088339A (en) * | 2023-08-24 | 2023-11-21 | 河南省氟基新材料科技有限公司 | Preparation method of difluoro sulfonyl imide salt |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311486A (en) * | 2013-05-14 | 2013-09-18 | 中南大学 | Organic-inorganic composite membrane as well as preparation and application thereof |
| CN104201417A (en) * | 2014-09-23 | 2014-12-10 | 中国人民解放军国防科学技术大学 | Li-S battery and Li-S reserve battery capable of performing impulsive discharge, and preparation methods thereof |
| JP5970815B2 (en) * | 2010-08-27 | 2016-08-17 | 東レ株式会社 | White laminated film manufacturing method and white laminated polyester film |
| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
| CN109546052A (en) * | 2018-09-29 | 2019-03-29 | 大连中比动力电池有限公司 | A kind of preparation method of perfluorinated sulfonic acid lithium coating diaphragm |
| CN109638349A (en) * | 2018-12-04 | 2019-04-16 | 中国科学院山西煤炭化学研究所 | A kind of organic-inorganic nanocomposite solid electrolyte diaphragm and its preparation method and application |
| CN109659606A (en) * | 2018-12-24 | 2019-04-19 | 燕山大学 | A kind of composite electrolyte membrane and preparation method thereof and lithium secondary battery |
| CN109742441A (en) * | 2018-12-05 | 2019-05-10 | 湖州天丰电源有限公司 | A kind of film-type composite solid electrolyte and preparation method thereof and solid lithium battery |
-
2019
- 2019-10-17 CN CN201910985702.2A patent/CN110783512B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5970815B2 (en) * | 2010-08-27 | 2016-08-17 | 東レ株式会社 | White laminated film manufacturing method and white laminated polyester film |
| CN103311486A (en) * | 2013-05-14 | 2013-09-18 | 中南大学 | Organic-inorganic composite membrane as well as preparation and application thereof |
| CN104201417A (en) * | 2014-09-23 | 2014-12-10 | 中国人民解放军国防科学技术大学 | Li-S battery and Li-S reserve battery capable of performing impulsive discharge, and preparation methods thereof |
| CN107645013A (en) * | 2016-07-22 | 2018-01-30 | 中国科学院物理研究所 | Compound quasi-solid electrolyte, its preparation method and the lithium battery or lithium ion battery containing it |
| CN109546052A (en) * | 2018-09-29 | 2019-03-29 | 大连中比动力电池有限公司 | A kind of preparation method of perfluorinated sulfonic acid lithium coating diaphragm |
| CN109638349A (en) * | 2018-12-04 | 2019-04-16 | 中国科学院山西煤炭化学研究所 | A kind of organic-inorganic nanocomposite solid electrolyte diaphragm and its preparation method and application |
| CN109742441A (en) * | 2018-12-05 | 2019-05-10 | 湖州天丰电源有限公司 | A kind of film-type composite solid electrolyte and preparation method thereof and solid lithium battery |
| CN109659606A (en) * | 2018-12-24 | 2019-04-19 | 燕山大学 | A kind of composite electrolyte membrane and preparation method thereof and lithium secondary battery |
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