CN1310483A - 凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法 - Google Patents
凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法 Download PDFInfo
- Publication number
- CN1310483A CN1310483A CN01108824A CN01108824A CN1310483A CN 1310483 A CN1310483 A CN 1310483A CN 01108824 A CN01108824 A CN 01108824A CN 01108824 A CN01108824 A CN 01108824A CN 1310483 A CN1310483 A CN 1310483A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- barrier film
- gel polymer
- diaphragm
- acetone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 25
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 17
- 239000005518 polymer electrolyte Substances 0.000 title claims description 17
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 11
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 230000004888 barrier function Effects 0.000 claims description 20
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 19
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000005516 engineering process Methods 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 239000004014 plasticizer Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000004513 sizing Methods 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 3
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000002931 mesocarbon microbead Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910015645 LiMn Inorganic materials 0.000 claims description 2
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003610 charcoal Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims 3
- 239000004811 fluoropolymer Substances 0.000 claims 2
- 229920002313 fluoropolymer Polymers 0.000 claims 2
- 239000011159 matrix material Substances 0.000 claims 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 239000011888 foil Substances 0.000 claims 1
- 239000011256 inorganic filler Substances 0.000 claims 1
- 229910003475 inorganic filler Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000741 silica gel Substances 0.000 abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 abstract description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229920006370 Kynar Polymers 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- FRCHCYFLGZRELU-UHFFFAOYSA-N butan-2-one;cyclohexanone Chemical compound CCC(C)=O.O=C1CCCCC1 FRCHCYFLGZRELU-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical class CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 229920005609 vinylidenefluoride/hexafluoropropylene copolymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
Abstract
本发明公开了一种凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法,本法关键在于使用精选的分散剂分别将硅胶增强超细粉、LiCoO2粉体、负极炭材料粉体均一地分布于电解质隔膜、正极膜片、负极膜片中,制备了性能优异的电池隔膜、正、负极膜片。使用本方法制备的含氟聚合物凝胶电解质隔膜、正、负极膜所制造的叠层式可充聚合物电池具有安全性好、容量大、电池放电能力强等优点,并且电池制造工艺简便、易于工业化。
Description
本发明公开一种凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法，涉及使用固体或凝胶型聚合物电解质作隔膜的可充锂电池的制造方法，属于聚合物锂离子电池的制造方法技术领域。
聚合物锂离子电池是1999年面世的新一代锂离子电池。在这种电池中，充电时，锂离子自含锂嵌入化合物阴极，通过一种离子导电物质(固体聚合物电解质或凝胶态聚合物电解质)进入阳极，放电时锂离子则从阳极溶下，再通过上述离子导电物质返回阴极，而外电路的电子则做相应的运动。由于电解质是固态的，能加工成薄膜，又可用铝塑包装膜封装，故聚合物锂离子电池较之通常液体锂离子电池具有许多优点，如无液体泄漏、电池安全性高、比能量密度高、形状灵活、可制成厚度小于1毫米的电池等。1995年，美国贝尔通信研究院(BellCommunications Research,Inc,)在其申请的专利中公布了具有上述优点的聚合物锂离子电池的制造方法(US Patent 5460904)。其电池制造方法的核心技术是聚合物电解质膜的制备技术(见US Patent 5296318和US Patent 5418091)。此法的要点是：首先将VDF/HFP共聚物、增塑剂、SiO2超细粉，混于丙酮(或甲乙酮)中，在50℃下制备合适的浆液，浇铸后先制得聚合物前体膜；然后在有机溶剂中抽提去增塑剂，从而生成具有一定微孔结构的薄膜；进而再将所得的干燥的微孔膜在惰性气氛条件下浸以1M LiPF6 EC/DMC(1∶1)溶液，在吸收电解质后，即制成最终凝胶态聚合物电解质。但是该法中所用SiO2超细粉不溶于丙酮等有机溶剂中，在此场合下构成多相的不稳定的分散系，故所得浇铸膜极不均匀，不能满足锂离子电池的需要。因此，如何将SiO2超细粉以微米级均匀分散在聚合物膜中，借此提高聚合物前体膜的机械强度、增强其在溶剂抽提操作时的抗皱性、最终聚合物电解质膜的导电性和电池的充放电性能，是至关重要的。
本发明的目的是提供一种凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法，应用此种凝胶聚合物电解质隔膜材料制造聚合物锂离子电池的方法。
本发明的技术解决方案如下：
1、二氧化硅超细粉的预处理：选取四乙二醇二甲醚(以下简称TEG)、壬基酚聚氧乙烯醚(OP-4、OP-8、OP-10、OP-15等)、平平加(平平加-10、平平加-15、平平加-20等)、硅烷偶合剂[(CH3O)3SiCH2CH2CH2NHCH2CH2NH2、(EtO)3SiCH2CH2CH2NH2和(CH3O)2SiHCH2CH2CH2NHCH2CH2NH2等]、钛系偶合剂(钛酸异丙酯衍生物)中的一种或几种混合物作为分散剂，通过加入所精选的分散剂到二氧化硅一丙酮(或丁酮)悬浮液中，在30-60℃下处理30分钟到1小时左右，从而使二氧化硅超细粉得以微米级团粒均匀地分散于聚合物基膜中。
2、聚合物电解质隔膜的制法
将100份重均分子量38×104道尔顿的VDF/HFP共聚物和150-200份增塑剂如邻苯二甲酸二丁酯(以下简称DBP)在50℃下溶于丙酮(或丁酮、环己酮、四氢呋喃、丁酮/异丁醇、丙酮/正丁醇等溶剂)。再将经上述手续处理过的40-60份纳米SiO2超微粉-丙酮的悬浮液加到上述聚合物溶液中，再充分混匀。之后，让该混合物在30℃下静置3-10分钟，接着以涂布机涂敷即可得填料分布十分均一的聚合物前体膜，涂膜厚度一般为20-100μm。
3、正极膜片之制法
将52-58份LiCoO2(或LiNiO2、LiMn2O4)与6-8份乙炔黑、11-13份上述VDF/HFP共聚物和24-26份DBP在丙酮中56℃下搅拌1-2小时制成浆液，再加入1份上述的分散剂(如壬基酚聚氧乙烯-10醚)调成均匀膏体后，将浆液涂敷于玻璃板或金属箔上，使溶剂挥发即成为正极片。片的厚度控制在180μm-200μm范围。
4、负极膜片的制法
将52-58份负极炭材料粉体(以下简称MCMB)与3份乙炔黑、12-15份VDF/HFP共聚物和26-29份增塑剂和1份上述分散剂(如壬基酚聚氧乙烯-10醚)于有机溶剂丙酮(或丁酮、丁酮\环己酮混合溶剂)中于50-56℃下搅拌1-2小时调成均匀浆料，然后涂敷于玻璃板或金属箔上即成。负极片厚在90-130μm范围。
5、叠层式(Lamilate)电池制法
首先，按设计容量要求，将以上制得的正、负极片和隔膜裁剪成一定的尺寸。经化学处理过和漂洗过的清洁的50μ厚的铜网和铝网也裁剪成同样的形状和大小，再在铜网和铝网上的一定部位上用超声焊接技术焊接上极耳。然后依次将正极集流体铝网、正极片、隔膜、负极片和负极集流体铜网逐层叠合起来，在100-120℃热压成五层一体化的薄片，接着进一步折叠到所需尺寸，再用热压机热压一次，使叠式电池的形状固定下来。然后，将这最终得到的电池浸泡于沸点为90-120℃的石油醚或甲醇中5-10分钟。取出后将其置于40℃真空烘箱中干燥1-2小时，接着将这些干燥过的电池转移到氩气循环手套箱中，灌入1M LiPF6 EC/DMC(1∶1)电解液，电池则活化完毕；最后以铝塑复合包装膜封装之，就成为电池。
与已知现有技术相比，采用本发明聚合物锂离子电池制造技术具有许多优点：
(1)采用本发明技术，隔膜制造工艺易行，硅胶(或Al2O3)
超细粉在浆液中易混合均一，所得隔膜质地均匀、力学
强度大，抽提时抗皱性好，室温电导率高。
(2)采用本发明技术，在隔膜生产中，还不必使用特制的纳
米硅胶，任何厂家生产的纳米硅胶均可。
(3)采用本发明技术，正、负极膜生产工艺简便、正、负极
膜质地更加均匀，显示更加优异的性能。
附图说明：
图1是平板纸状电池的剖面图：
1、极耳
2、正极集流体
3、正极膜片
4、隔膜
5、负极膜片
6、负极集流体
7、极耳
图2是“叠层式”电池经充电后不同倍率的放电图
1、2C倍率放电曲线
2、1C倍率放电曲线
3、0.5C倍率放电曲线
4、0.2C倍率放电曲线
下面结合实施例对本发明作进一步说明
实施例1
将0.25g纳米级SiO2超微粉(MNIP-0210)中，依次加入5ml丙酮(AR级)，0.05ml OP-15。在56℃下回流30分钟。后冷至室温再加入10ml丙酮，0.50g分子量为38×104道尔顿和HFP含量为12(重量)％的VDF/HFP共聚物(Kynar 2801)和1.00ml DBP。重新回流搅拌，待完全溶解后继续搅拌30分钟。之后冷却釜温至30℃。聚合物溶液静置3分钟后，在玻璃板上浇铸。溶剂挥发后，得略有淡淡纹理的SiO2粉体分布十分均一且强韧的聚合物膜，其膜厚在70μ左右。该膜经己烷抽提后，灌入1M LiClO4碳酸丙烯酯(以下简称PC)电解质溶液。其16℃室温电导率为1.6x10-3S/cm。
实施例2
将52份LiCoO2(美国OMG公司产品)与8份乙炔黑(焦作鑫达公司产品)、13份分子量为38×104道尔顿和HFP含量为12(重量)％的VDF/HFP共聚物(Kynar Flex 2801)、26份DBP和1份壬基酚聚氧乙烯-10醚(OP-10)置于带盖的釜中，以丙酮作介质在56℃下高速搅拌制备均匀膏体正极浆料。浆料混匀后，将其冷到30℃。然后以涂布机涂布，溶剂挥发后即得到正极膜片，膜片的厚度控制为220μm，每100cm2正极膜片重4.50g。
实施例3
将52份负极MCMB(鞍山热能院产品)与3份乙炔黑、15份VDF/HFP共聚物(Kynar 2801)、29份增塑剂DBP和1份OP-10置于带有回流冷凝器的玻璃釜中以有机溶剂丙酮在50℃下高速搅拌调成均匀浆料。浆料冷到30℃后，静置5分钟，然后以涂布机涂布。溶剂挥发后即得负极膜片，膜片厚度为120μm，每100cm2负极膜片重1.90g。
实施例4
裁剪长31.5cm宽65cm矩形负极集流体铜网(约50μ厚，美国Exmet公司产品)。再将它浸于3％HNO3和H2SO4混合液中10秒钟以去掉其上油污和氧化物。接着用水漂洗、烘干。然后以2％VDF\HFP共聚物(Kynar 2801)溶液(其中含氟共聚物对增塑剂之比为1∶1)浸渍之，取出晾干备用。
同样大小的正极集流体铝网先以0.25％的三聚磷酸钠和十二烷基苯磺酸钠水溶液清洗，此后则按处理铜网相似方法逐步处理。然后，分别在正、负极集流体铜网和铝网的适当部位用超声焊机焊上极耳。
实施例5
叠层式可充电池按以下方法组装：
先将例4负极集流体铜网平整地铺在刚性的导热良好的铝板上，再依次在其上铺上形状和大小相同的例3负极膜片、例1电解质隔膜片(隔膜的尺寸应略比正、负极膜片大些，以防止它们偶然短路接触)，例2正极膜片和例4正极集流体铝网。最后，在其上再铺上第二块刚性的导热良好的铝板。
然后将叠式电池及其上、下铝板一起移到135℃烘箱中加上重物进行热压，热压时间以恰好能达到板间热平衡和实现各膜片间熔融为宜。压毕，取出，卸掉重物，冷至室温。平板纸状电池如图1所示。接着进一步将电池折叠到所需尺寸，再按上述热压手续热压一次，使其形状固定下来。
实施例6
将例5“叠层式”电池置于不锈钢制成的金属容器中，不断泵入沸点在90-120℃的石油醚或甲醇在40-45℃下处理10分钟。处理毕，以氮气排去抽提溶剂。取出电池再将它们置于40℃真空烘箱中干燥1小时。之后，将干燥的电池转移到氩气循环手套箱中以注液机灌入1MLiPF6 EC\DMC(1∶1)电解液。最后用电池封装机复以铝塑包装膜，经热压“封口”，即制得最终电池。
该电池的充、放电性能如图2所示。
Claims (9)
1．一种凝胶态聚合物电解质隔膜的制造方法，包括以下工艺：将100份含氟共聚物和150-200份增塑剂如邻苯二甲酸二丁酯在50℃下溶于有机溶剂中配成溶液，接着加入经分散剂处理过的20-60份的无机填料增强粉于少量的丙酮或丁酮中的悬浮液，经充分匀浆后，冷到30℃，以涂布法制成25-80μm厚的薄膜。
2．根据权利要求1所述的凝胶态聚合物电解质隔膜的制造方法，其特征在于以同样含氟聚合物为基体，易与隔膜层压在一起的正极膜：按52-58份LiCoO2(或LiNiO2、LiMn2O4)粉末、6-8份乙炔黑、11-13份共聚物、24-26份DBP和1份本发明分散剂之配料比将复合正极混合物在有机溶剂中制成均匀浆料，然后用涂布法将浆料涂布于玻璃板或金属箔上，于30-60℃下干燥，一起制得正极膜片。
3．根据权利要求1所述的凝胶态聚合物电解质隔膜的制造方法，其特征在于以同样含氟聚合物为基体，易与隔膜层压在一起的负极膜：按52-58份负极炭材料粉体(MCMB)、3份乙炔黑、12-15份共聚物、26-29份DBP和1份本发明分散剂如壬基酚聚氧乙烯-10醚的配料比将复合负极混合物在于有机溶剂中制成均匀浆料，然后用涂布法将浆料涂布于玻璃板或金属箔上，于30-60℃下干燥，制得负极膜片。
4．根据权利要求1所述的凝胶态聚合物电解质隔膜，其特征在于：纳米SiO2粉体分散剂，包括四乙二醇二甲醚、壬基酚聚氧乙烯醚、平平加、和硅烷偶合剂。
5．根据权利要求1所述的凝胶态聚合物电解质隔膜，其特征是：含氟共聚物为偏氟乙烯和六氟丙烯共聚物，该共聚物具有13×104-38×104道尔顿的分子量和具有8-30％重量的六氟丙烯含量，最好六氟丙烯的重量百分含量为10-12％。
6．根据权利要求1所述的凝胶态聚合物电解质隔膜，其特征在于：所述的有机溶剂为丙酮、丁酮、环己酮、四氢呋喃和环己烷/丁酮、丙酮/异丁醇、丁酮/正丁醇、N-甲基吡咯烷酮/丙酮等混合溶剂。
7．根据权利要求1所述的凝胶态聚合物电解质隔膜，其特征在于；所述增塑剂包括邻苯二甲酸二丁酯(DBP)、邻苯二甲酸二甲酯(DMP)、碳酸丙烯酯(PC)等。
8．一种层叠式锂离子电池的制造方法，其特征在于：将上述生产工艺制成的正极集流体铝网、正极膜片、隔膜、负极膜片和负极集流体铜网，裁剪成一定尺寸的矩形于130-135℃下热压复合成五层一体化的薄片，接着将上述复合薄片折叠到所需尺寸大小，再用热压机热压一次，使其形状固定下来；然后以沸点为90-120℃的石油醚或甲醇抽提去添加的DBP，干燥后再注入电解液的方法，制成所需锂离子电池。
9．根据权利要求8的制造方法制造的电池。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01108824A CN1310483A (zh) | 2001-01-09 | 2001-02-20 | 凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法 |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01106067 | 2001-01-09 | ||
| CN01106067.0 | 2001-01-09 | ||
| CN01108824A CN1310483A (zh) | 2001-01-09 | 2001-02-20 | 凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1310483A true CN1310483A (zh) | 2001-08-29 |
Family
ID=25740283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01108824A Pending CN1310483A (zh) | 2001-01-09 | 2001-02-20 | 凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1310483A (zh) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100456551C (zh) * | 2004-12-01 | 2009-01-28 | 索尼株式会社 | 电池 |
| CN102130364A (zh) * | 2011-02-12 | 2011-07-20 | 中南大学 | 一种锂硫二次电池体系用凝胶型聚合物电解质及制备方法 |
| CN102208680A (zh) * | 2011-05-05 | 2011-10-05 | 中国东方电气集团有限公司 | 凝胶电解质及其制备方法、和相应的正极、锂硫电池 |
| CN101512824B (zh) * | 2006-09-07 | 2011-12-07 | 株式会社Lg化学 | 凝胶聚合物电解质和含有该凝胶聚合物电解质的电化学装置 |
| AP2606A (en) * | 2009-11-16 | 2013-03-04 | Impala Platinum Refineries Ltd | An autoclave baffle |
| CN103247819A (zh) * | 2012-02-06 | 2013-08-14 | 三星Sdi株式会社 | 锂二次电池 |
| CN105280868A (zh) * | 2015-09-30 | 2016-01-27 | 中国科学院长春应用化学研究所 | 一种偏氟乙烯-六氟丙烯共聚物/SiO2复合膜及其制备方法和应用 |
| US9437896B2 (en) | 2012-02-07 | 2016-09-06 | Samsung Sdi Co., Ltd. | Method of preparing lithium secondary battery |
| CN109830770A (zh) * | 2019-02-18 | 2019-05-31 | 中南大学 | 具有监控功能的超大容量储能锂离子电池 |
-
2001
- 2001-02-20 CN CN01108824A patent/CN1310483A/zh active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100456551C (zh) * | 2004-12-01 | 2009-01-28 | 索尼株式会社 | 电池 |
| CN101512824B (zh) * | 2006-09-07 | 2011-12-07 | 株式会社Lg化学 | 凝胶聚合物电解质和含有该凝胶聚合物电解质的电化学装置 |
| US8318361B2 (en) | 2006-09-07 | 2012-11-27 | Lg Chem, Ltd. | Gel polymer electrolyte and electrochemical device comprising the same |
| AP2606A (en) * | 2009-11-16 | 2013-03-04 | Impala Platinum Refineries Ltd | An autoclave baffle |
| CN102130364A (zh) * | 2011-02-12 | 2011-07-20 | 中南大学 | 一种锂硫二次电池体系用凝胶型聚合物电解质及制备方法 |
| CN102208680A (zh) * | 2011-05-05 | 2011-10-05 | 中国东方电气集团有限公司 | 凝胶电解质及其制备方法、和相应的正极、锂硫电池 |
| CN103247819A (zh) * | 2012-02-06 | 2013-08-14 | 三星Sdi株式会社 | 锂二次电池 |
| US9450223B2 (en) | 2012-02-06 | 2016-09-20 | Samsung Sdi Co., Ltd. | Lithium secondary battery |
| CN103247819B (zh) * | 2012-02-06 | 2016-12-28 | 三星Sdi株式会社 | 锂二次电池 |
| US9437896B2 (en) | 2012-02-07 | 2016-09-06 | Samsung Sdi Co., Ltd. | Method of preparing lithium secondary battery |
| CN105280868A (zh) * | 2015-09-30 | 2016-01-27 | 中国科学院长春应用化学研究所 | 一种偏氟乙烯-六氟丙烯共聚物/SiO2复合膜及其制备方法和应用 |
| CN109830770A (zh) * | 2019-02-18 | 2019-05-31 | 中南大学 | 具有监控功能的超大容量储能锂离子电池 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1126185C (zh) | 非水电解质电池用电极 | |
| CN108899579B (zh) | 一种自交联复合固态电解质的制备及其构成的全固态锂离子电池 | |
| Chou et al. | Small things make a big difference: binder effects on the performance of Li and Na batteries | |
| KR102003291B1 (ko) | 다공성 보호층이 형성된 전극, 이의 제조방법 및 이를 적용한 리튬 이차전지 | |
| CN1332457C (zh) | 电化学元件 | |
| EP2672545B1 (en) | Battery separator and preparation method thereof, and lithium ion battery | |
| CN112397762B (zh) | 一种固态电池 | |
| US20050285080A1 (en) | Electrode composite particles, electrode and electrochemical element, method of manufacturing the electrode composite particles, electrode manufacturing method, electrochemical element manufacturing method | |
| EP1032059B1 (en) | Secondary battery, and its production process | |
| CN1394363A (zh) | 非水电解质二次电池 | |
| JP2008103259A (ja) | 固体電解質シート、電極シート及びそれを用いた全固体二次電池 | |
| JP2004186089A (ja) | 電極形成用塗布液、電極及び電気化学素子、並びに、電極形成用塗布液の製造方法、電極の製造方法及び電気化学素子の製造方法 | |
| CN1783571A (zh) | 电池 | |
| EP3480878A1 (en) | Positive electrode additive and preparation method therefor, positive electrode plate and secondary lithium ion battery | |
| US20020119371A1 (en) | Method of fabricating electrode foils and galvanic elements fabricated from the method | |
| WO2002061872A1 (en) | A multi-layered polymer electrolyte and lithium secondary battery comprising the same | |
| JP7536069B2 (ja) | 電極、それを含むリチウム電池及びその製造方法 | |
| KR102094993B1 (ko) | 리튬 이차전지용 음극 및 이를 채용한 리튬 이차전지 | |
| CN1310483A (zh) | 凝胶态聚合物电解质隔膜及叠层式锂离子电池的制造方法 | |
| WO2020119321A1 (en) | Separator for long cycle life lithium sulfur batteries | |
| CN111584929A (zh) | 一种固态电解质及制备方法和锂电池 | |
| WO2022112735A1 (en) | Electrochemical cell | |
| CN114361570A (zh) | 一种钠电池及其制备方法 | |
| CN111816842B (zh) | 含有钝化保护膜的锂电极及其制备方法和锂离子电池 | |
| CN1835262A (zh) | 正极活性材料组合物、正极片及锂离子电池 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| ASS | Succession or assignment of patent right |
Owner name: JILIN PROVINE HUARUAN TECHNOLOGY CO., LTD. Free format text: FORMER OWNER: JIDA CHAOYUE S+.T DEVELOPMENT CO., LTD., CHANGCHUN Effective date: 20020325 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20020325 Address after: 130061, room 2403, union business service center, 11 Xi'an Road, Jilin, Changchun Applicant after: Jilin Huaruan Technology Co., Ltd. Address before: Spark Road in high tech Development Zone in Jilin Province, 130012 street, No. 20 Changchun Applicant before: Jida Chaoyue S&.T Development Co., Ltd., Changchun |
|
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Addressee: Jilin Huaruan Technology Co., Ltd. Document name: Notification before expiration of term |
|
| ASS | Succession or assignment of patent right |
Owner name: BIKE BATTERY CO., LTD., SHENZHEN CITY Free format text: FORMER OWNER: JILIN PROVINE HUARUAN TECHNOLOGY CO., LTD. Effective date: 20040423 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20040423 Address after: Kwai Chung Town Industrial Zone Shenzhen city Longgang Zhenda 518000 District ten building Applicant after: Shenzhen Bak Battery Co., Ltd. Address before: 130061, room 2403, union business service center, 11 Xi'an Road, Jilin, Changchun Applicant before: Jilin Huaruan Technology Co., Ltd. |
|
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Document name: Deemed as a notice of withdrawal |
|
| C57 | Notification of unclear or unknown address | ||
| DD01 | Delivery of document by public notice |
Document name: Notice of conformity |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |