CN105118947A - Method for preparing lithium ion battery diaphragm - Google Patents
Method for preparing lithium ion battery diaphragm Download PDFInfo
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- CN105118947A CN105118947A CN201510577173.4A CN201510577173A CN105118947A CN 105118947 A CN105118947 A CN 105118947A CN 201510577173 A CN201510577173 A CN 201510577173A CN 105118947 A CN105118947 A CN 105118947A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 21
- SRFGYPCGVWVBTC-UHFFFAOYSA-N lithium;dihydrogen borate;oxalic acid Chemical compound [Li+].OB(O)[O-].OC(=O)C(O)=O SRFGYPCGVWVBTC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 239000005518 polymer electrolyte Substances 0.000 claims abstract description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 13
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 11
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 9
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000010416 ion conductor Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract 1
- 229920005597 polymer membrane Polymers 0.000 description 6
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001523 electrospinning Methods 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical group FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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)
- Secondary Cells (AREA)
- Cell Separators (AREA)
Abstract
本发明涉及一种锂离子电池隔膜的制备方法，包括：（1）聚合物电解质聚丙稀酸草酸硼酸锂的制备，原料聚乙烯醇、硼酸、二甲基亚砜、草酸和无水碳酸锂的摩尔比为2∶（0.85-1.15）∶2∶（0.475-0.55）∶（0.85-1.15）；（2）静电纺聚偏氟乙烯六氟丙烯隔膜和聚合物电解质聚丙稀酸草酸硼酸锂的复合，将电纺膜平铺于玻璃板上，上表面用体积比为1∶1的乙醇水溶液浸湿。本发明制备的锂离子复合电池隔膜优异的机械性能和热稳定性能，同时分解电压高达4.9V，较商用隔膜的4.3V有大幅的提升，离子电导率较商用隔膜提升2倍，锂离子迁移数为0.65，所制备锂离子电池表现出良好的循环性能和倍率性能，锂离子电池的安全性能得到进一步提升。The invention relates to a preparation method of lithium ion battery diaphragm, comprising: (1) preparation of polymer electrolyte polyacrylic acid lithium oxalate borate, raw materials polyvinyl alcohol, boric acid, dimethyl sulfoxide, oxalic acid and anhydrous lithium carbonate The molar ratio is 2:(0.85-1.15):2:(0.475-0.55):(0.85-1.15); (2) The composite of electrospun polyvinylidene fluoride hexafluoropropylene separator and polymer electrolyte polyacrylic acid lithium oxalate borate , the electrospun membrane was flatly spread on a glass plate, and the upper surface was wetted with an aqueous ethanol solution with a volume ratio of 1:1. The lithium ion composite battery diaphragm prepared by the present invention has excellent mechanical properties and thermal stability, and at the same time, the decomposition voltage is as high as 4.9V, which is greatly improved compared with 4.3V of the commercial diaphragm, and the ion conductivity is 2 times higher than that of the commercial diaphragm. is 0.65, the prepared lithium-ion battery exhibits good cycle performance and rate performance, and the safety performance of the lithium-ion battery is further improved.
Description
技术领域 technical field
本发明涉及电池隔膜领域，特别是涉及一种锂离子电池隔膜的制备方法。 The invention relates to the field of battery separators, in particular to a preparation method of lithium-ion battery separators.
背景技术 Background technique
单离子导体聚合物电解质聚丙稀酸草酸硼酸锂具有较好的单离子导电行为。但其室温电导率较低（小于10-5Scm-1），力学性能较差，不能满足锂离子电池应用的需求。为了改善这两种聚合物电解质的性能，受商用三层结构隔膜的启发，设想将其与其它商用聚合物膜复合，通过两种聚合物膜的性质互补，获得具有较优性能的复合凝胶聚合物电解质以满足锂离子电池的需要。 Single-ion conductor polymer electrolyte polyacrylic acid lithium oxalate borate has good single-ion conduction behavior. However, its conductivity at room temperature is low (less than 10 -5 Scm -1 ), and its mechanical properties are poor, which cannot meet the needs of lithium-ion battery applications. In order to improve the performance of these two polymer electrolytes, inspired by the commercial three-layer structure separator, it is conceived to combine it with other commercial polymer membranes, and obtain a composite gel with better performance by complementing the properties of the two polymer membranes. Polymer electrolytes meet the needs of Li-ion batteries.
研究者对聚偏氟乙烯六氟丙烯作为凝胶聚合物电解质进行了广泛研究，结果显示其电导率（大于10-4Scm-1）可以满足锂离子电池应用的需要，但孔隙率、孔的均一性等性质与聚合物膜的生产工艺有很大关系。常见的聚合物电解质膜的生产工艺有溶液浇注法、增塑剂萃取法、相转化法及电纺法等。相比于其它几种方法，电纺法制备的聚合物膜由于内部表现出完全相互连接的孔结构而显示出较高的孔隙率，另外，电纺工艺操作简单，可以很容易制备不同孔径范围（从纳米级到微米级）的聚合物膜，在锂子电池领域显示出较好的应用前景。为此，将单离子导体聚丙稀酸草酸硼酸锂同商用电纺聚偏氟乙烯六氟丙烯隔膜复合，复合得到类似于celgard2320PP/PE/PP结构的隔膜，使得两种膜之间的性质互补，期望得到力学性能好，安全性高，电导率满足应用要求，电化学性能优异并且具有高锂离子迁移数的聚合物电解质体系。 Researchers have conducted extensive research on polyvinylidene fluoride hexafluoropropylene as a gel polymer electrolyte, and the results show that its conductivity (greater than 10 -4 Scm -1 ) can meet the needs of lithium-ion battery applications, but the porosity, pore Properties such as uniformity have a lot to do with the production process of the polymer film. Common production processes of polymer electrolyte membranes include solution casting, plasticizer extraction, phase inversion, and electrospinning. Compared with several other methods, the polymer membrane prepared by electrospinning shows a higher porosity due to the fully interconnected pore structure inside. In addition, the electrospinning process is simple to operate and can easily prepare different pore size ranges. Polymer films (from nanoscale to micron scale) show good application prospects in the field of lithium-ion batteries. To this end, the single-ion conductor polyacrylic acid lithium oxalate borate was combined with commercial electrospun polyvinylidene fluoride hexafluoropropylene separator to obtain a separator similar to celgard2320PP/PE/PP structure, which made the properties of the two membranes complementary , it is expected to obtain a polymer electrolyte system with good mechanical properties, high safety, electrical conductivity meeting application requirements, excellent electrochemical performance and high lithium ion migration number.
发明内容 Contents of the invention
本发明的目的是提供一种锂离子电池隔膜的制备方法，具体包括以下步骤： The object of the present invention is to provide a kind of preparation method of lithium-ion battery diaphragm, specifically comprises the following steps:
（1）单离子导体聚丙稀酸草酸硼酸锂膜的制备：在烧瓶中加入聚乙烯醇、硼酸和二甲基亚砜，室温搅拌至澄清，加热升温至85℃，保温6h后依次慢慢加入二水合草酸和无水碳酸锂，投料过程避免气泡产生过快反应物溢出，投料完毕，搅拌1h后升温至105℃反应20h，冷却至室温。将反应物倒入培养皿，放在加热板上85℃加热36h将溶剂挥发成膜，即得产物聚丙稀酸草酸硼酸锂。其中聚乙烯醇、硼酸、二甲基亚砜、草酸和碳酸锂按特定摩尔比2：（0.85-1.15）：2：（0.475-0.55）：（0.85-1.15）进行投料。 (1) Preparation of single-ion conductor polyacrylic acid lithium oxalate borate membrane: Add polyvinyl alcohol, boric acid and dimethyl sulfoxide into a flask, stir at room temperature until clarified, heat up to 85°C, keep warm for 6 hours, and then slowly add Dihydrated oxalic acid and anhydrous lithium carbonate. During the feeding process, avoid bubbles from being generated too quickly and the reactant overflows. After the feeding is completed, the temperature is raised to 105°C for 20 hours after stirring for 1 hour, and cooled to room temperature. The reactant was poured into a petri dish, placed on a heating plate and heated at 85°C for 36 hours to evaporate the solvent and form a film to obtain the product polyacrylic acid lithium oxalate borate. Among them, polyvinyl alcohol, boric acid, dimethyl sulfoxide, oxalic acid and lithium carbonate are fed according to a specific molar ratio of 2: (0.85-1.15): 2: (0.475-0.55): (0.85-1.15).
（2）静电纺聚偏氟乙烯六氟丙烯隔膜和聚合物电解质聚丙稀酸草酸硼酸锂的复合：将电纺膜平铺于:玻璃板上，上表面用体积比为1:1的乙醇水溶液浸湿，将制备好的聚合物膜平铺在电纺膜上，膜上表面亦用乙醇水溶液润湿，将另一层电纺膜盖于其上。操作完毕，将制备的湿膜夹于两块干净的玻璃板之间，置于烘箱干燥，即得复合膜。 (2) Compositing of electrospun polyvinylidene fluoride hexafluoropropylene separator and polymer electrolyte polyacrylic acid lithium oxalate borate: spread the electrospun membrane on a glass plate, and use ethanol aqueous solution with a volume ratio of 1:1 on the upper surface After soaking, spread the prepared polymer membrane on the electrospun membrane, wet the upper surface of the membrane with ethanol aqueous solution, and cover another layer of electrospun membrane on it. After the operation is completed, the prepared wet film is sandwiched between two clean glass plates, and dried in an oven to obtain a composite film.
所述步骤（1）中，聚丙稀酸草酸硼酸锂膜厚度为20-40μm。 In the step (1), the polyacrylic acid lithium oxalate borate film has a thickness of 20-40 μm.
所述步骤（1）聚乙烯醇、硼酸、二甲基亚砜、草酸和碳酸锂摩尔比优选为2：（0.9-1.10）：2：（0.475-0.55）：（0.95-1.10）。 In the step (1), the molar ratio of polyvinyl alcohol, boric acid, dimethyl sulfoxide, oxalic acid and lithium carbonate is preferably 2:(0.9-1.10):2:(0.475-0.55):(0.95-1.10).
所述步骤（2）中电纺膜厚度为15-30μm，孔隙率为70-80%。 In the step (2), the thickness of the electrospun membrane is 15-30 μm, and the porosity is 70-80%.
所述步骤（2）中，所得复合膜为50-100μm。 In the step (2), the obtained composite film is 50-100 μm.
聚偏氟乙烯六氟丙烯作为凝胶聚合物电解质的电导率大于10-4Scm-1，可以满足锂离子电池应用的需要，电纺法制备的聚合物膜由于内部表现出完全相互连接的孔结构而显示出较高的孔隙率，工艺操作简单，可以很容易制备不同孔径范围（从纳米级到微米级）的聚合物膜，将单离子导体聚丙稀酸草酸硼酸锂同商用电纺聚偏氟乙烯六氟丙烯隔膜复合，复合得到类似于celgard2320PP/PE/PP结构的隔膜，使得两种膜之间的性质互补，制备得到的锂离子复合电池隔膜展现出优异的机械性能（MD:2400kg/cm2,TD:2400kg/cm2）和热稳定性能（电解液活化后复合隔膜在130℃下加热1h的剩余质量为加热前质量的88%，优于传统celgard2730d的50%），同时分解电压高达4.9V，较商用隔膜的4.3V有大幅的提升，离子电导率较商用隔膜提升2倍，锂离子迁移数为0.65，所制备锂离子电池表现出良好的循环性能和倍率性能，锂离子电池的安全性能得到进一步提升。 The conductivity of polyvinylidene fluoride hexafluoropropylene as a gel polymer electrolyte is greater than 10 -4 Scm -1 , which can meet the needs of lithium-ion battery applications. The polymer membrane prepared by electrospinning shows completely interconnected pores inside The structure shows high porosity, the process operation is simple, and it is easy to prepare polymer membranes with different pore sizes (from nanometer to micrometer). Composite vinylidene fluoride hexafluoropropylene diaphragm, compounded to obtain a diaphragm similar to celgard2320PP/PE/PP structure, so that the properties of the two films are complementary, and the prepared lithium-ion composite battery diaphragm exhibits excellent mechanical properties (MD: 2400kg /cm 2 , TD: 2400kg/cm 2 ) and thermal stability (after the electrolyte is activated, the remaining mass of the composite separator heated at 130°C for 1 hour is 88% of the mass before heating, which is better than 50% of the traditional celgard2730d), while decomposing The voltage is as high as 4.9V, which is greatly improved compared with the 4.3V of commercial separators. The ion conductivity is 2 times higher than that of commercial separators, and the lithium ion migration number is 0.65. The prepared lithium-ion batteries show good cycle performance and rate performance. The safety performance of the battery has been further improved.
具体实施方式 Detailed ways
以下通过具体实施例对本发明作进一步详细说明。 The present invention will be described in further detail below through specific examples.
实施例1 Example 1
（1）单离子导体聚丙稀酸草酸硼酸锂膜的制备：在100ml圆底烧瓶中加入200mg聚乙烯醇、148mg硼酸和20ml二甲基亚砜，室温搅拌至澄清，加热升温至85℃，保温6h后依次慢慢加入300mg二水合草酸和88mg无水碳酸锂，投料过程避免气泡产生过快反应物溢出，投料完毕，搅拌1h后升温至105℃反应20h，冷却至室温。将反应物倒入直径为10cm的培养皿，放在加热板上85℃加热36h将溶剂挥发成膜，即得厚度为22μm产物聚丙稀酸草酸硼酸锂。其中聚乙烯醇、硼酸、二甲基亚砜、草酸和碳酸锂按摩尔比2：1：2：0.5：1进行投料。 (1) Preparation of single ion conductor polyacrylic acid lithium oxalate borate film: Add 200 mg polyvinyl alcohol, 148 mg boric acid and 20 ml dimethyl sulfoxide into a 100 ml round bottom flask, stir at room temperature until clear, heat up to 85 °C, keep warm After 6 hours, slowly add 300mg of oxalic acid dihydrate and 88mg of anhydrous lithium carbonate in turn. During the feeding process, avoid bubbles from being generated too quickly and the reactants overflow. The reactant was poured into a petri dish with a diameter of 10 cm, placed on a heating plate and heated at 85°C for 36 hours to evaporate the solvent to form a film, and the product polyacrylic acid lithium oxalate borate with a thickness of 22 μm was obtained. Among them, polyvinyl alcohol, boric acid, dimethyl sulfoxide, oxalic acid and lithium carbonate are fed in a molar ratio of 2:1:2:0.5:1.
（2）静电纺聚偏氟乙烯六氟丙烯隔膜和聚合物电解质聚丙稀酸草酸硼酸锂的复合：将孔隙率为70%，厚度为15μm的商业电纺膜平铺于一干净玻璃板上，上表面用体积比为1:1的乙醇水溶液浸湿，将制备好的聚合物膜平铺在电纺膜上，膜上表面亦用乙醇水溶液润湿，将另一层电纺膜盖于其上。操作完毕，将制备的湿膜夹于两块干净的玻璃板之间，置于烘箱85℃干燥36h，即得厚度为52μm复合膜。 (2) Compositing of electrospun polyvinylidene fluoride hexafluoropropylene separator and polymer electrolyte polyacrylic acid lithium oxalate borate: a commercial electrospun membrane with a porosity of 70% and a thickness of 15 μm was laid flat on a clean glass plate, The upper surface was wetted with ethanol aqueous solution with a volume ratio of 1:1, and the prepared polymer film was spread on the electrospun membrane, and the upper surface of the membrane was also wetted with ethanol aqueous solution, and another layer of electrospun membrane was covered on it. superior. After the operation, the prepared wet film was sandwiched between two clean glass plates, and dried in an oven at 85°C for 36 hours to obtain a composite film with a thickness of 52 μm.
制备的锂离子复合电池隔膜展现出优异的机械性能（MD:2400kg/cm2，TD:2400kg/cm2）和热稳定性能（电解液活化后复合隔膜在130℃下加热1h的剩余质量为加热前质量的88%，优于传统celgard2730d的50%），同时分解电压高达4.9V，较商用隔膜的4.3V有大幅的提升，离子电导率较商用隔膜提升2倍，锂离子迁移数为0.65。 The prepared lithium-ion composite battery separator exhibits excellent mechanical properties (MD: 2400kg/cm 2 , TD: 2400kg/cm 2 ) and thermal stability (after the electrolyte is activated, the remaining mass of the composite separator heated at 130°C for 1 hour is the 88% of the former quality, which is better than 50% of the traditional celgard2730d), and the decomposition voltage is as high as 4.9V, which is greatly improved compared with the 4.3V of the commercial separator. The ion conductivity is 2 times higher than that of the commercial separator, and the lithium ion migration number is 0.65.
实施例2 Example 2
（1）单离子导体聚丙稀酸草酸硼酸锂膜的制备：在100ml圆底烧瓶中加入200mg聚乙烯醇、148mg硼酸和20ml二甲基亚砜，室温搅拌至澄清，加热升温至85℃，保温6h后依次慢慢加入300mg二水合草酸和88mg无水碳酸锂，投料过程避免气泡产生过快反应物溢出，投料完毕，搅拌1h后升温至105℃反应20h，冷却至室温。将反应物倒入直径为10cm的培养皿，放在加热板上85℃加热36h将溶剂挥发成膜，即得厚度为22μm产物聚丙稀酸草酸硼酸锂。其中聚乙烯醇、硼酸、二甲基亚砜、草酸和碳酸锂按摩尔比2：1：2：0.5：1进行投料。 (1) Preparation of single ion conductor polyacrylic acid lithium oxalate borate film: Add 200 mg polyvinyl alcohol, 148 mg boric acid and 20 ml dimethyl sulfoxide into a 100 ml round bottom flask, stir at room temperature until clear, heat up to 85 °C, keep warm After 6 hours, slowly add 300mg of oxalic acid dihydrate and 88mg of anhydrous lithium carbonate in turn. During the feeding process, avoid bubbles from being generated too quickly and the reactants overflow. The reactant was poured into a petri dish with a diameter of 10 cm, placed on a heating plate and heated at 85°C for 36 hours to evaporate the solvent to form a film, and the product polyacrylic acid lithium oxalate borate with a thickness of 22 μm was obtained. Among them, polyvinyl alcohol, boric acid, dimethyl sulfoxide, oxalic acid and lithium carbonate are fed in a molar ratio of 2:1:2:0.5:1.
（2）静电纺聚偏氟乙烯六氟丙烯隔膜和聚合物电解质聚丙稀酸草酸硼酸锂的复合：将孔隙率为75%，厚度为15μm的商业电纺膜平铺于一干净玻璃板上，上表面用体积比为1:1的乙醇水溶液:浸湿，将制备好的聚合物膜平铺在电纺膜上，上表面亦用乙醇水溶液润湿，将另一层电纺膜盖于其上。操作完毕，将制备的湿膜夹于两块干净的玻璃板之间，置于烘箱85℃干燥36h，即得厚度为52μm复合膜。 (2) Compositing of electrospun polyvinylidene fluoride hexafluoropropylene separator and polymer electrolyte polyacrylic acid lithium oxalate borate: a commercial electrospun membrane with a porosity of 75% and a thickness of 15 μm was laid flat on a clean glass plate, The upper surface is wetted with an ethanol aqueous solution with a volume ratio of 1:1, and the prepared polymer film is flatly spread on the electrospun membrane, and the upper surface is also wetted with an ethanol aqueous solution, and another layer of electrospun membrane is covered on it. superior. After the operation, the prepared wet film was sandwiched between two clean glass plates, and dried in an oven at 85°C for 36 hours to obtain a composite film with a thickness of 52 μm.
制备的锂离子复合电池隔膜展现出优异的机械性能（MD:2000kg/cm2，TD:2000kg/cm2）和热稳定性能（电解液活化后复合隔膜在130℃下加热1h的剩余质量为加热前质量的86%，优于传统celgard2730d的50%），同时分解电压高达4.8V，较商用隔膜的4.3V有大幅的提升，离子电导率较商用隔膜提升2.2倍，锂离子迁移数为0.70。 The prepared lithium-ion composite battery separator exhibits excellent mechanical properties (MD: 2000kg/cm 2 , TD: 2000kg/cm 2 ) and thermal stability (after the electrolyte is activated, the remaining mass of the composite separator heated at 130°C for 1 hour is 86% of the former quality, which is better than 50% of the traditional celgard2730d), and the decomposition voltage is as high as 4.8V, which is greatly improved compared with 4.3V of commercial separators. The ion conductivity is 2.2 times higher than that of commercial separators, and the lithium ion migration number is 0.70.
实施例3 Example 3
（1）单离子导体聚丙稀酸草酸硼酸锂膜的制备：在100ml圆底烧瓶中加入200mg聚乙烯醇、148mg硼酸和20ml二甲基亚砜，室温搅拌至澄清，加热升温至85℃，保温6h后依次慢慢加入300mg二水合草酸和88mg无水碳酸锂，投料过程避免气泡产生过快反应物溢出，投料完毕，搅拌1h后升温至105℃反应20h，冷却至室温。将反应物倒入直径为10cm的培养皿，放在加热板上85℃加热36h将溶剂挥发成膜，即得厚度为22μm产物聚丙稀酸草酸硼酸锂。其中聚乙烯醇、硼酸、二甲基亚砜、草酸和碳酸锂按摩尔比2：1：2：0.5：1进行投料。 (1) Preparation of single ion conductor polyacrylic acid lithium oxalate borate film: Add 200 mg polyvinyl alcohol, 148 mg boric acid and 20 ml dimethyl sulfoxide into a 100 ml round bottom flask, stir at room temperature until clear, heat up to 85 °C, keep warm After 6 hours, slowly add 300mg of oxalic acid dihydrate and 88mg of anhydrous lithium carbonate in turn. During the feeding process, avoid bubbles from being generated too quickly and the reactants overflow. The reactant was poured into a petri dish with a diameter of 10 cm, placed on a heating plate and heated at 85°C for 36 hours to evaporate the solvent to form a film, and the product polyacrylic acid lithium oxalate borate with a thickness of 22 μm was obtained. Among them, polyvinyl alcohol, boric acid, dimethyl sulfoxide, oxalic acid and lithium carbonate are fed in a molar ratio of 2:1:2:0.5:1.
（2）静电纺聚偏氟乙烯六氟丙烯隔膜和聚合物电解质聚丙稀酸草酸硼酸锂的复合：将孔隙率为80%，厚度为15μm的商业电纺膜平铺于一干净玻璃板上，上表面用体积比为1:1的乙醇水溶液浸湿，将制备好的聚合物膜平铺在电纺膜上，上表面亦用乙醇水溶液润湿，将另一层电纺膜盖于其上。操作完毕，将制备的湿膜夹于两块干净的玻璃板之间，置于烘箱85℃干燥36h，即得厚度为52μm复合膜。 (2) Compositing of electrospun polyvinylidene fluoride hexafluoropropylene separator and polymer electrolyte polyacrylic acid lithium oxalate borate: a commercial electrospun membrane with a porosity of 80% and a thickness of 15 μm was laid flat on a clean glass plate, The upper surface is wetted with ethanol aqueous solution with a volume ratio of 1:1, and the prepared polymer film is spread on the electrospun membrane, and the upper surface is also wetted with ethanol aqueous solution, and another layer of electrospun membrane is covered on it. . After the operation, the prepared wet film was sandwiched between two clean glass plates, and dried in an oven at 85°C for 36 hours to obtain a composite film with a thickness of 52 μm.
制备的锂离子复合电池隔膜展现出优异的机械性能（MD:1900kg/cm2，TD:1900kg/cm2）和热稳定性能（电解液活化后复合隔膜在130℃下加热1h的剩余质量为加热前质量的85%，优于传统celgard2730d的50%），同时分解电压高达4.7V，较商用隔膜的4.3V有大幅的提升，离子电导率较商用隔膜提升2.4倍，锂离子迁移数为0.72。 The prepared lithium-ion composite battery separator exhibits excellent mechanical properties (MD: 1900kg/cm 2 , TD: 1900kg/cm 2 ) and thermal stability (after the electrolyte is activated, the remaining mass of the composite separator heated at 130°C for 1 hour is 85% of the former quality, which is better than 50% of the traditional celgard2730d), and the decomposition voltage is as high as 4.7V, which is greatly improved compared with 4.3V of commercial separators. The ion conductivity is 2.4 times higher than that of commercial separators, and the lithium ion migration number is 0.72.
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| CN112481829A (en) * | 2020-11-16 | 2021-03-12 | 华中科技大学 | Single-ion conductor polymer electrolyte composite diaphragm, and preparation method and application thereof |
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