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WO2020094090A1 - Séparateur composite à sélectivité ionique, son procédé de préparation et son application - Google Patents

Séparateur composite à sélectivité ionique, son procédé de préparation et son application Download PDF

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Publication number
WO2020094090A1
WO2020094090A1 PCT/CN2019/116215 CN2019116215W WO2020094090A1 WO 2020094090 A1 WO2020094090 A1 WO 2020094090A1 CN 2019116215 W CN2019116215 W CN 2019116215W WO 2020094090 A1 WO2020094090 A1 WO 2020094090A1
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Prior art keywords
ion
selective composite
coating
lithium
inorganic ceramic
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PCT/CN2019/116215
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English (en)
Chinese (zh)
Inventor
何平
王鹏飞
周豪慎
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苏州迪思伏新能源科技有限公司
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Publication of WO2020094090A1 publication Critical patent/WO2020094090A1/fr

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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
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • 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
    • H01M50/44—Fibrous material
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the technical field of battery separators, in particular to an ion selective composite separator, its preparation method and application.
  • the current commercial lithium-ion battery has a maximum actual energy density of about 240Wh ⁇ kg -1 , which is only higher than that of the first-generation lead-acid battery (40Wh ⁇ kg -1 ) 5 times higher.
  • the original battery system has an urgent need for the development of new battery systems with high energy density due to its inherent theoretical upper limit.
  • Lithium-sulfur battery is an ideal choice for the next-generation battery composed of S cathode and Li anode. Its theoretical energy density is as high as 2600Wh ⁇ kg -1 , and it is environmentally friendly and low cost.
  • the technical problem to be solved by the present invention is to provide an ion-selective composite membrane, which can effectively suppress the shuttle of polysulfide ions and the generation of lithium dendrites.
  • the present invention provides an ion-selective composite membrane, which includes a polymer porous layer, a carboxymethylcellulose sodium coating and an inorganic ceramic coating respectively coated on both sides of the polymer porous layer .
  • the sodium carboxymethyl cellulose coating is located on the positive side of the separator
  • the inorganic ceramic coating is located on the negative side of the separator.
  • the sodium carboxymethyl cellulose is a series of modified products of natural cellulose, including commonly used modification methods of natural cellulose such as etherification or esterification, the production process is mature, and the output Rich, and rich in natural sources, environmentally friendly, very suitable for large-scale production.
  • a preferred solution in the present invention is that the thickness of the inorganic ceramic coating is 0.01-40 ⁇ m, and the thickness of the sodium carboxymethyl cellulose coating is 0.01-20 ⁇ m.
  • a preferred solution in the present invention is that the total thickness of the ion-selective composite separator is 0.1-100 ⁇ m.
  • the inorganic ceramic coating is a coating formed of one or more components of Al 2 O 3 , other transition metal oxides or sulfides.
  • other transition metal oxides or sulfides include CeO 2 , MoS 2 , ZrO 2 , MoO 2 , and ZnO. More preferably, the inorganic ceramic coating is Al 2 O 3 coating.
  • the polymer porous layer is a polypropylene (PP) layer or a polyethylene (PE) layer; or includes at least two layers of alternately stacked PP layers and PE layers.
  • PP polypropylene
  • PE polyethylene
  • the polymer porous layer can also be made of other commercially available polymer films, including but not limited to polyester films, cellulose films, polyimide films, and polyamide films.
  • Another aspect of the present invention provides a method for preparing the above ion-selective composite membrane, including the following steps:
  • porous polymer layer coated with an inorganic ceramic coating on one side dissolve sodium carboxymethylcellulose in a solvent, apply the resulting solution to the other side of the porous polymer layer, and bake at 35 to 80 ° C 1 ⁇ 72h, the ion selective composite membrane is obtained.
  • a preferred solution in the present invention is to apply the sodium carboxymethyl cellulose solution by a doctor blade coating method, the gap width of the doctor blade is 0.1-30 ⁇ m, and the speed of the doctor blade is 0.1-10 cm / s.
  • the inorganic ceramic coating is prepared through the following steps:
  • the inorganic ceramic powder, binder and solvent are prepared into a slurry, which is sprayed on the surface of the porous polymer layer to obtain an inorganic ceramic coating; wherein, the mass ratio of the inorganic ceramic powder to the binder is 1: 99 ⁇ 30 : 70.
  • a preferred solution in the present invention is that the binder is PVDF and / or sodium alginate.
  • a preferred solution in the present invention is that the solvent used for dissolving sodium carboxymethyl cellulose and inorganic ceramic powder is water and / or an organic solvent; wherein the organic solvent is selected from N-methylpyrrolidone (NMP), N, One or more of N-dimethylformamide (DMF), tetrahydrofuran (THF), acetonitrile, and acetone.
  • NMP N-methylpyrrolidone
  • DMF N-dimethylformamide
  • THF tetrahydrofuran
  • acetonitrile acetone
  • the preferred solution in the present invention is to spray the slurry onto the surface of the polymer porous layer using an industrial transfer or extrusion spray method.
  • Another aspect of the present invention provides the application of the ion-selective composite separator in lithium batteries, especially in lithium-sulfur batteries and lithium-lithium symmetric batteries.
  • Step 1 S powder and Ketchen black are mixed by hand grinding, the resulting mixed material is packed in glass bottles, pre-fired in Ar atmosphere at 155 °C for 0.5-10 hours; take out and continue grinding for 0.5-3 hours, then at 200 °C It is further annealed in an Ar gas atmosphere, and finally a highly conductive composite material of S @ ⁇ ⁇ ⁇ is obtained.
  • the ratio of S to Ketjen Black is 95: 5 ⁇ 50: 50.
  • Step 2 Grind S @ ⁇ ⁇ ⁇ , conductive agent (SP) uniformly in the ratio of 6: 1 ⁇ 9: 1, then add the pre-prepared glue solution and stir for 0.5 ⁇ 12h to form a uniform and stable slurry;
  • SP conductive agent
  • Step 3 Apply the slurry from the above step to the aluminum current collector, vacuum dry at 35-80 ° C overnight, cut into circular electrode pieces with a diameter of 0.2-1.5 cm using a mold, and assemble the button battery for use.
  • Step 4 Assemble the negative electrode case, lithium sheet, composite separator, electrolyte, S electrode sheet, and positive electrode case into a button cell.
  • Step 1 Cut the metal Li sheet into small discs with a preset diameter, the diameter must be smaller than the diameter of the cut composite diaphragm;
  • Step 2 Assemble the negative electrode casing, the cut lithium sheet, the composite separator, the electrolyte, the cut lithium sheet, and the positive electrode casing into a button cell.
  • the CMC coating on the positive electrode side can adsorb polysulfide ions through chemical bonds to form a polysulfide ion adsorption layer, which blocks the polysulfide ions through the double action of electric field and physics; at the same time, it suppresses to a certain extent
  • the migration of anions in LiTFSI improves the migration number of Li + and also makes the contact between the separator and the electrode closer, shortening the migration distance of ions in the electrode;
  • the inorganic ceramic coating on the negative electrode side serves as a stable interface layer , Maintaining a uniform lithium ion anode interface flux, which facilitates the uniform deposition of lithium ions on the anode and avoids the formation of lithium anode cracks.
  • the synergistic effect of the two can further avoid a series of problems caused by the so-called "shuttle effect" of lithium-sulfur batteries, such as reduced Coulomb efficiency, increased negative side reactions, and abrupt capacity decay.
  • the test of the symmetrical battery also showed that the composite separator facilitated the uniform deposition of lithium ions, and the surface of the lithium metal electrode showed a uniform surface morphology. The method is simple to operate, is beneficial to large-scale preparation, and is helpful for the wide commercial application of high energy density lithium-sulfur batteries.
  • FIG. 1 (a) is a schematic structural view of the application of the composite separator of the present invention in a lithium-sulfur battery
  • Figures 1 (b)-(e) are the surface topography of three kinds of separators; where, b is the scanning electron microscope (SEM) image of the CMC coated surface, c is the SEM image of the pure polymer film, and d and e are SEM image of polymer surface and Al 2 O 3 surface coated with Al 2 O 3 separator;
  • SEM scanning electron microscope
  • FIG. 2 is a schematic diagram of the blocking effect of the three membranes in FIG. 1 on polysulfide ions; where, a is a pure polymer membrane, b is an Al 2 O 3 coated membrane, and c is Al 2 O 3 and CMC coated Diaphragm
  • Example 3 is a graph of the cycle performance and Coulomb efficiency of the lithium-sulfur battery in Example 2, the test current is 0.5C;
  • the three types of separators are pure polymer separators, Al 2 O 3 -polymer separators and Al 2 O 3 -polymers -CMC composite diaphragm;
  • Figure 4 is a graph of the adsorption effect of CMC coating on polysulfide; a and b are the comparison before and after the addition of CMC powder, and cf is the test of the coated membrane soaked in polysulfide solution and then repeatedly rinsed with DME XPS map;
  • Example 5 is a charge-discharge diagram of a lithium-lithium symmetric battery in Example 3, in which the deposition capacity is 4 mAh ⁇ cm -2 and the current is 20 mA ⁇ cm -2 ;
  • FIG. 6 is a SEM image of the lithium metal surface obtained after disassembly of the lithium-lithium symmetric battery in Example 3 after the same number of charge and discharge cycles; where a and b are the lithium metal surfaces on both sides of the pure polymer separator, c, d are Al 2 O 3 - Li 2 O 3 metal surface of the polymer surface and the surface of an Al polymer membrane, e, f are Al 2 O 3 - CMC side and Al 2 O polymer membrane -CMC Lithium metal surface on 3 sides;
  • Example 7 is the Li + lithium symmetrical battery in Example 3 using the AC impedance and potentiostat chronoamperometry to test the number of Li + migration, where a, b, and c are the AC impedance graphs before and after polarization of the three membranes, respectively.
  • the specific migration number of Li + of the three separators calculated by the formula;
  • FIG. 8 is a graph of the surface change of the Al 2 O 3 coating after baking at 120 °C and 150 °C for 1 hour.
  • Example 1 Preparation of ion-selective composite separator and lithium-sulfur battery
  • An ion-selective composite separator comprising a sodium carboxymethyl cellulose (CMC) coating applied on the positive side of the separator, an Al 2 O 3 coating applied on the negative side of the separator, and a polymer porous layer in the middle.
  • the thickness of the polymer porous layer is 12 ⁇ m
  • the thickness of the CMC coating is 10 ⁇ m
  • the thickness of the Al 2 O 3 coating is 4 ⁇ m.
  • the preparation method of the ion selective composite membrane is as follows:
  • Step 1 S powder and Ketjen Black are mixed by hand grinding, the obtained mixed materials are packed in glass bottles, pre-fired in Ar atmosphere at 155 °C for 5h; take out and continue grinding for 1h, and then in Ar atmosphere at 200 °C After further annealing for 2h, S @ ⁇ ⁇ ⁇ 's highly conductive composite material was finally obtained.
  • the mass ratio of S to Ketjen Black is 70:30.
  • Step 2 Grind S @ ⁇ ⁇ ⁇ and conductive agent SP at a ratio of 8: 1, then add the pre-prepared 5% PVDF glue solution and stir for 2h to form a uniform and stable slurry;
  • Step 3 Coat the obtained slurry on an aluminum current collector, vacuum dry at 60 ° C overnight, and cut into circular electrode pieces with a diameter of 1.2 cm using a mold;
  • Step 4 Assemble the negative electrode case, lithium sheet, composite separator, electrolyte, S electrode sheet, and positive electrode case into a button cell.
  • FIG. 1 (a) is a schematic diagram of the lithium-sulfur battery prepared in Example 1.
  • FIG. The cross-sectional SEM images show the thickness of each coating and polymer layer.
  • the thickness of the polymer layer is 12 ⁇ m
  • the thickness of the CMC coating is 10 ⁇ m
  • the thickness of the Al 2 O 3 coating is 4 ⁇ m.
  • Figure 1 (b)-(e) shows that the coating has a porous structure, which can allow the smooth passage of ions.
  • Figure 2 shows the blocking effect of different coating layers on polysulfide ions.
  • Figure 2 (a) is a pure polymer membrane, and polysulfide ions can easily shuttle to the other side of the mold; while Figure 2 (b) is a polymer membrane coated with Al 2 O 3 coating only , Showing a better barrier effect than pure polymer membranes, but some polysulfide ions will still shuttle after 24h; and the composite membrane with Al 2 O 3 and CMC coating in Fig. 2 (c) remains at 24h Good polysulfide barrier effect.
  • Example 2 Preparation of ion-selective composite separator and lithium-sulfur battery
  • An ion selective composite separator comprising a sodium carboxymethyl cellulose (CMC) coating applied on the positive side of the separator, an Al 2 O 3 coating on the negative side and a porous polymer layer in the middle, the polymer
  • the thickness of the porous layer is 12 ⁇ m
  • the thickness of the CMC coating is 2 ⁇ m
  • the thickness of the Al 2 O 3 coating is 4 ⁇ m.
  • the preparation method of the ion selective composite membrane is as follows:
  • CMC sodium carboxymethyl cellulose
  • Step 1 S powder and Ketjen Black are mixed by hand grinding, the obtained mixed materials are packed in glass bottles, pre-fired in Ar atmosphere at 155 °C for 5h; take out and continue grinding for 1h, and then in Ar atmosphere at 200 °C After further annealing for 2h, S @ ⁇ ⁇ ⁇ 's highly conductive composite material was finally obtained.
  • the ratio of S to Ketjen Black is 70:30.
  • Step 2 Grind S @ ⁇ ⁇ ⁇ , conductive agent (SP) at a ratio of 8: 1, then add the pre-prepared 5% PVDF glue solution and stir for 2h to form a uniform and stable slurry;
  • SP conductive agent
  • Step 3 Apply the slurry from the above step to the aluminum current collector, vacuum dry at 60 ° C overnight, cut into circular electrode pieces with a mold, and assemble a 1.2cm diameter button cell for use.
  • Step 4 Assemble the negative electrode case, lithium sheet, composite separator, electrolyte, S electrode sheet and positive electrode case into a coin cell, and perform relevant electrochemical tests such as charge and discharge.
  • FIG. 3 is a graph of electrochemical performance of the lithium-sulfur battery of Example 2.
  • FIG. It can be seen from the figure that after 300 cycles of 0.5C, the capacity of pure polymer membrane, Al 2 O 3 coated membrane, Al 2 O 3 and CMC coated membrane can be maintained at 626.3, 681.3 and 812.2mAh ⁇ g -1 , in which Al 2 O 3 and CMC-coated separators can maintain a specific capacity of 718.2 mAh ⁇ g -1 in 500 cycles, showing good cycle stability.
  • the change graph of Coulomb efficiency also shows that the pure polymer membrane has a strong shuttle phenomenon, resulting in severe capacity overcharge.
  • CMC has a strong adsorption effect on polysulfide, and the adsorbed polysulfide further inhibits the shuttle of polysulfide through the action of physical and electric fields;
  • Figure 4 (f) shows that the surface of CMC adsorbs firmly Layer of polysulfide, some of which are oxidized to other sulfur-containing substances during the test; at the same time, c, d, and e in the figure also show that CMC has rich functional groups such as hydroxyl, carboxyl, and ether groups. The layer can effectively adsorb and inhibit the polysulfide shuttle to provide theoretical support.
  • An ion-selective composite separator comprising a sodium carboxymethyl cellulose (CMC) coating applied on the positive side of the separator, an Al 2 O 3 coating applied on the negative side, and a polymer porous layer in the middle, said The thickness of the polymer porous layer was 12 ⁇ m, the thickness of the CMC coating was 2 ⁇ m, and the thickness of the Al 2 O 3 coating was 4 ⁇ m.
  • CMC sodium carboxymethyl cellulose
  • the preparation method of the ion selective composite membrane is as follows:
  • CMC sodium carboxymethyl cellulose
  • Step 1 Cut the metal Li piece into a small 1.2cm diameter wafer
  • Step 2 Assemble the negative electrode case, the cut lithium sheet, the composite separator, the electrolyte, the cut lithium sheet, and the positive electrode case into a button cell, and perform electrochemically related characterization of the symmetric battery.
  • FIG. 5 is a charge-discharge curve of the lithium-lithium symmetric battery prepared in this example, in which the deposition capacity is 4 mAh ⁇ cm ⁇ 2 and the current is 20 mA ⁇ cm ⁇ 2 .
  • Al 2 O 3 and CMC-coated separators have the smallest charge-discharge overpotential, about 55mV, and can be stably charged and discharged for 900h at a large current of 20mA ⁇ cm -2 ; for comparison, only Al 2 overpotential separator O 3 coating of about 160mV, and the pure polymer membrane overpotential of 280mV. This shows that the CMC coating can significantly reduce the overpotential of the battery, possibly because it can make the electrode and the separator contact more closely, reducing the charge transfer resistance.
  • FIG. 6 shows the surface morphology of Li metal after disassembling the lithium-lithium symmetrical batteries with different separators after cycling 10 cycles under the conditions of 4 mAh ⁇ cm -2 and current of 20 mA ⁇ cm -2 .
  • Fig. 6 (a) and (b) are pure polymer separators, and it can be clearly seen that dendrites are generated due to uneven lithium deposition; Fig.
  • FIG. 6 (c) is only the polymer side lithium of Al 2 O 3 coated separators The surface also shows uneven lithium deposition;
  • Figures 6 (d) and (f) are the Al 2 O 3 coated separator and Al 2 O 3 , and the Al 2 O 3 surface Li metal surface shape of the CMC coated separator The appearance is relatively uniform, and the Li surface on the CMC side in Figure 6 (e) appears as a unified whole, showing a uniform Li deposition; further proof that the Al 2 O 3 and CMC coated separators have good lithium -Lithium symmetric battery performance.
  • the ion-selective composite separator of the present invention can suppress the shuttle effect of the lithium-sulfur battery on the one hand, improve the cycle stability and coulombic efficiency of the lithium-sulfur battery; on the other hand, make the separator and electrode pads contact more closely and reduce the charge
  • the transfer resistance enables Li + to be deposited uniformly at the interface; meanwhile, Al 2 O 3 coating can effectively improve the safety performance of the separator.
  • the scheme can also be extended to battery systems such as lithium air and traditional cathode material systems, and can also be applied to other battery systems that use lithium metal anodes, which can reduce the interface impedance and improve the interface stability of the battery;
  • the design is easy to operate, safe and stable during battery operation, and is an effective method to improve the performance of commercial batteries.

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Abstract

L'invention concerne un séparateur composite à sélectivité ionique, comprenant : une couche poreuse polymère ; et un revêtement de carboxyméthylcellulose sodique et un revêtement céramique inorganique respectivement revêtus sur deux côtés de la couche poreuse polymère. L'invention concerne en outre un procédé de préparation du séparateur composite à sélectivité ionique et une application du séparateur composite à sélectivité ionique dans une batterie au lithium. Le séparateur composite à sélectivité ionique de la présente invention peut supprimer efficacement le transfert d'ions polysulfure et la génération de dendrites de lithium.
PCT/CN2019/116215 2018-11-09 2019-11-07 Séparateur composite à sélectivité ionique, son procédé de préparation et son application WO2020094090A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115842214A (zh) * 2022-10-18 2023-03-24 福州大学 一种具有筛分效应耐高压低自放电隔膜、制备方法及应用
CN117801346A (zh) * 2024-02-29 2024-04-02 西北工业大学 高机械强度和高锂离子通量的轻薄改性pe隔膜制备方法
CN117977115A (zh) * 2024-03-28 2024-05-03 西北工业大学 一种可抑制钠枝晶生长的电池隔膜及其制备方法和应用

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109599524B (zh) * 2018-11-09 2021-04-06 苏州迪思伏新能源科技有限公司 离子选择性复合隔膜及其制备方法和应用
CN110112349A (zh) * 2019-05-14 2019-08-09 东华大学 一种锂硫电池隔膜及其制备方法
CN114944538B (zh) * 2022-07-07 2024-04-16 贵州航盛锂能科技有限公司 钠离子电池陶瓷隔膜及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5371227A (en) * 1976-12-07 1978-06-24 Seiko Instr & Electronics Method of manufacturing separator for alkaline battery
CN105514328A (zh) * 2016-01-13 2016-04-20 浙江天能能源科技有限公司 一种锂离子电池用陶瓷隔膜及其制备方法
CN105810981A (zh) * 2016-04-21 2016-07-27 常州大学 一种离子选择性聚合物复合膜及其制备方法
CN108172739A (zh) * 2017-12-22 2018-06-15 哈尔滨工业大学深圳研究生院 锂硫电池的附加自组装层的羧基化隔膜及制备方法
CN109599524A (zh) * 2018-11-09 2019-04-09 苏州迪思伏新能源科技有限公司 离子选择性复合隔膜及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104916802B (zh) * 2015-04-09 2017-11-07 厦门大学 一种复合隔膜及其应用
CN107665966A (zh) * 2016-07-27 2018-02-06 中国科学院大连化学物理研究所 一种锂硫电池
US20180226635A1 (en) * 2017-02-07 2018-08-09 Shi Yuan Lithium ion battery positive electrode composition and preparation method thereof
CN107834007A (zh) * 2017-11-14 2018-03-23 欣旺达电子股份有限公司 隔膜和锂离子电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5371227A (en) * 1976-12-07 1978-06-24 Seiko Instr & Electronics Method of manufacturing separator for alkaline battery
CN105514328A (zh) * 2016-01-13 2016-04-20 浙江天能能源科技有限公司 一种锂离子电池用陶瓷隔膜及其制备方法
CN105810981A (zh) * 2016-04-21 2016-07-27 常州大学 一种离子选择性聚合物复合膜及其制备方法
CN108172739A (zh) * 2017-12-22 2018-06-15 哈尔滨工业大学深圳研究生院 锂硫电池的附加自组装层的羧基化隔膜及制备方法
CN109599524A (zh) * 2018-11-09 2019-04-09 苏州迪思伏新能源科技有限公司 离子选择性复合隔膜及其制备方法和应用

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115842214A (zh) * 2022-10-18 2023-03-24 福州大学 一种具有筛分效应耐高压低自放电隔膜、制备方法及应用
CN117801346A (zh) * 2024-02-29 2024-04-02 西北工业大学 高机械强度和高锂离子通量的轻薄改性pe隔膜制备方法
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