CN117586011B - 一种高性能石墨负极材料制备工艺 - Google Patents
一种高性能石墨负极材料制备工艺 Download PDFInfo
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- CN117586011B CN117586011B CN202410065455.5A CN202410065455A CN117586011B CN 117586011 B CN117586011 B CN 117586011B CN 202410065455 A CN202410065455 A CN 202410065455A CN 117586011 B CN117586011 B CN 117586011B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 39
- 239000010439 graphite Substances 0.000 title claims abstract description 39
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 229910021382 natural graphite Inorganic materials 0.000 claims abstract description 11
- 238000007792 addition Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims description 58
- 229910021641 deionized water Inorganic materials 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 238000002156 mixing Methods 0.000 claims description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000000706 filtrate Substances 0.000 claims description 26
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 239000003607 modifier Substances 0.000 claims description 20
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 20
- -1 aminopropyl Chemical group 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 17
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 17
- 229920005575 poly(amic acid) Polymers 0.000 claims description 16
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 12
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims description 11
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 10
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- 239000004317 sodium nitrate Substances 0.000 claims description 10
- 235000010344 sodium nitrate Nutrition 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 6
- UNIBAJHMJGXVHL-UHFFFAOYSA-N 3-phenylbenzene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C(C=2C=CC=CC=2)=C1C(O)=O UNIBAJHMJGXVHL-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002153 silicon-carbon composite material Substances 0.000 abstract description 8
- 230000001105 regulatory effect Effects 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 229910021389 graphene Inorganic materials 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 4
- 239000011229 interlayer Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000003396 thiol group Chemical class [H]S* 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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Abstract
本发明公开了一种高性能石墨负极材料制备工艺,通过对天然石墨处理后,再进行氮掺杂处理,氮掺杂能够引入更多的储存锂位点并扩大石墨烯层间距,使得充放电过程中锂离子的脱嵌更容易,并负载氧化锡,氧化锡能够增加负极材料的比容量,通过聚酰胺酸盐热亚胺化再高温碳化,在表面形成碳硅复合层包覆,碳硅复合层的包覆能够抑制预处理石墨在脱嵌锂时产生体积膨胀,进而防止了氧化锡粉化和脱落,表面的碳硅复合层为多孔结构,能够增加锂离子的扩散通道,保护改性填料的在电解液中的稳定,提高负极材料的倍率性能,通过中间体1和环氧笼型聚倍半硅氧烷的加入来调节表面的碳硅复合层的结构,能够进一步提升电极的比容量。
Description
技术领域
本发明涉及负极材料制备技术领域,具体涉及一种高性能石墨负极材料制备工艺。
背景技术
锂离子电池作为高效的电能容纳和变换容器,即电能的储能场所也是电能的释放设备,能通过可逆的电化学插层反应达到电能和化学能之间的相互转换目的。同时,高电能量荷载是锂离子电池的关键特性,锂离子电池被广泛应用于各种形式的耗电设备的电能供给。锂离子电池未来应用面广泛,主要有两个应用领域,即应用于移动式储能***和固定式大型储能***的电能存贮和供能。锂离子电池作为高效的电能容纳和变换容器,即电能的储能场所也是电能的释放设备,能通过可逆的电化学插层反应达到电能和化学能之间的相互转换目的,现有石墨的倍率性能较差,已经越来越却难以满足快充市场需求,特别是在电动汽车高速发展的时代背景下,石墨倍率性能差的技术缺陷会严重制约电动汽车的普及。
发明内容
本发明的目的在于提供一种高性能石墨负极材料制备工艺,解决的现阶段负极材料长时间使用后会持续按膨胀坍塌的问题,导致电池使用寿命低。
本发明的目的可以通过以下技术方案实现:
一种高性能石墨负极材料制备工艺,具体包括如下步骤:
步骤A1:将二苯二氯硅烷、KH572和去离子水混合,在转速为200-300r/min,温度为60-70℃的条件下,搅拌10-15min后,加入浓硫酸和1,3-双(氨丙烷基)四甲基二硅醚,进行反应4-6h后,调节pH至中性,制得中间体1,将去离子水、四乙基氢氧化铵和异丙醇混合均匀,在转速为200-300r/min,温度为30-35℃的条件下,搅拌并加入KH560,搅拌4-6h后,升温至75-80℃,进行反应15-20h,过滤去除滤液,制得环氧笼型聚倍半硅氧烷;
步骤A2:将中间体1、环氧笼型聚倍半硅氧烷和DMF混合均匀,在转速为150-200r/min,温度为30-40℃,pH值为11-12的条件下,进行反应5-7h,减压蒸馏,制得改性剂,将改性剂、3,3,4,4-联苯四甲酸二酐和N,N-二甲基乙酰胺混合,在转速为300-500r/min,温度为0-3℃的条件下,搅拌2-4h,升温至20-25℃,加入三乙胺,继续反应3-4h后,将反应产物加入丙酮中,静置2-3h后,过滤去除滤液,制得聚酰胺酸盐;
步骤A3:将聚酰胺酸盐、改性填料、三乙胺和去离子水混合,在转速为500-800r/min,365nm紫外光照射的条件下,搅拌1-1.5h后,倒入模具中,在温度为零下196℃的条件下,保温20-25h,再在温度为零下15℃,真空度为2-3Pa的条件下,干燥10-15h,放入管式炉中,在温度为220-250℃的条件下,保温2-3h,升温至950-1000℃,碳化处理3-5h,制得高性能石墨负极材料。
进一步,步骤A1所述的二苯二氯硅烷、KH572去离子水和1,3-双(氨丙烷基)四甲基二硅醚的用量比为2mmol:1mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、KH572和1,3-双(氨丙烷基)四甲基二硅醚质量和的1-1.5%,去离子水、四乙基氢氧化铵、异丙醇和KH560的质量比为10:0.21:32:40.25。
进一步,步骤A2所述的中间体1和环氧笼型聚倍半硅氧烷的摩尔比为8:1,改性剂、3,3,4,4-联苯四甲酸二酐和三乙胺的摩尔比为1:8:8.3。
进一步,步骤A3所述的聚酰胺酸盐、改性填料和去离子水的用量比为10g:2g:0.3g:200mL。
进一步,所述的改性填料由如下步骤制成:
步骤B1:将天然石墨、硝酸钠和浓硫酸混合均匀,在转速为150-200r/min,温度为0-3℃的条件下,搅拌并加入高锰酸钾,搅拌2-3h后,升温至35-40℃,加入去离子水,加入完毕后升温至95-98℃,搅拌30-40min,加入双氧水,继续搅拌1-1.5h,过滤去除滤液,制得预处理石墨;
步骤B2:将预处理石墨、聚乙烯吡咯烷酮和甲醇混合均匀,加入六水合硝酸锌和2-甲基咪唑,在转速为200-300r/min,温度为20-25℃的条件下,搅拌4-6h,过滤去除滤液,将底物在温度为800-850℃,氩气保护的条件下,保温4-6h后,在盐酸溶液中,浸泡10-15h,过滤洗涤至中性,制得改性石墨;
步骤B3:将草酸亚锡分散在去离子水中,加入柠檬酸溶液混合均匀,调pH为中性,加入改性石墨,在频率为20-30kHz的条件下,超声处理3-5h,过滤去除滤液,将底物在温度为400-450℃的条件下,保温2-3h,制得改性基体,将改性基体分散在乙醇中,在转速为200-300r/min,温度为50-60℃的条件下,搅拌并加入3-巯丙基三乙氧基硅烷和去离子水,进行反应1-1.5h,制得改性填料。
进一步,步骤B1所述的天然石墨、硝酸钠、浓硫酸、高锰酸钾、去离子水和双氧水的用量比为1g:0.5g:26mL:3g:46mL:10mL,双氧水质量分数为30%。
进一步,步骤B2所述的预处理石墨、聚乙烯吡咯烷酮、甲醇、六水合硝酸锌和2-甲基咪唑的用量比为40mg:50mg:40mL:0.73g:0.85g,盐酸溶液的浓度为2mol/L。
进一步,步骤B3所述的草酸亚锡、去离子水、柠檬酸溶液和改性石墨的用量比为1.2g:2.5mL:5mL:1g,3-巯丙基三乙氧基硅烷的用量为改性石墨质量的3%。
本发明的有益效果:本发明制备的一种高性能石墨负极材料以二苯二氯硅烷和KH572为原料先水解,再在浓硫酸的作用下与1,3-双(氨丙烷基)四甲基二硅醚聚合,形成氨基封端的聚硅氧烷,制得中间体1,将KH560水解聚合,形成笼型聚倍半硅氧烷,将中间体1和环氧笼型聚倍半硅氧烷在碱性条件下反应,使得中间体1上的氨基和环氧笼型聚倍半硅氧烷上的环氧基反应,形成以笼型硅氧烷为中心的超支结构,制得改性剂,将改性剂与3,3,4,4-联苯四甲酸二酐反应,3,3,4,4-联苯四甲酸二酐开环与改性剂上的氨基反应,以笼型硅氧烷为中心形成聚酰酸盐结构,制得聚酰胺酸盐,将聚酰胺酸盐和改性填料共混搅拌,并用365nm紫外光照射,使得聚酰胺酸盐上的双键与改性填料上的巯基接枝,形成有机包覆无机结构,再升温使得有机分子链热亚胺化,最后高温碳化,形成碳包覆,制得改性填料,改性填料以天然石墨烯为原料处理,制得预处理石墨,将预处理石墨用2-甲基咪唑处理形成氮掺杂状态,制得改性石墨,将改性石墨通过草酸亚锡水热法在表面附着氧化锡,最后用KH572表面处理使得表面机制巯基,制得改性填料,该改性填料通过对天然石墨处理后,再进行氮掺杂处理,氮掺杂能够引入更多的储存锂位点并扩大石墨烯层间距,使得充放电过程中锂离子的脱嵌更容易,并负载氧化锡,氧化锡能够增加负极材料的比容量,通过聚酰胺酸盐热亚胺化再高温碳化,在表面形成碳硅复合层包覆,碳硅复合层的包覆能够抑制预处理石墨在脱嵌锂时产生体积膨胀,进而防止了氧化锡粉化和脱落,表面的碳硅复合层为多孔结构,能够增加锂离子的扩散通道,保护改性填料的在电解液中的稳定,提高负极材料的倍率性能,通过中间体1和环氧笼型聚倍半硅氧烷的加入来调节表面的碳硅复合层的结构,能够进一步提升电极的比容量。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其它实施例,都属于本发明保护的范围。
实施例1
一种高性能石墨负极材料制备工艺,具体包括如下步骤:
步骤A1:将二苯二氯硅烷、KH572和去离子水混合,在转速为200r/min,温度为60℃的条件下,搅拌10min后,加入浓硫酸和1,3-双(氨丙烷基)四甲基二硅醚,进行反应4h后,调节pH至中性,制得中间体1,将去离子水、四乙基氢氧化铵和异丙醇混合均匀,在转速为200r/min,温度为30℃的条件下,搅拌并加入KH560,搅拌4h后,升温至75℃,进行反应15h,过滤去除滤液,制得环氧笼型聚倍半硅氧烷;
步骤A2:将中间体1、环氧笼型聚倍半硅氧烷和DMF混合均匀,在转速为150r/min,温度为30℃,pH值为11的条件下,进行反应5h,减压蒸馏,制得改性剂,将改性剂、3,3,4,4-联苯四甲酸二酐和N,N-二甲基乙酰胺混合,在转速为300r/min,温度为0℃的条件下,搅拌2h,升温至20℃,加入三乙胺,继续反应3h后,将反应产物加入丙酮中,静置2h后,过滤去除滤液,制得聚酰胺酸盐;
步骤A3:将聚酰胺酸盐、改性填料、三乙胺和去离子水混合,在转速为500r/min,365nm紫外光照射的条件下,搅拌1h后,倒入模具中,在温度为零下196℃的条件下,保温20h,再在温度为零下15℃,真空度为2Pa的条件下,干燥10h,放入管式炉中,在温度为220℃的条件下,保温2h,升温至950℃,碳化处理3h,制得高性能石墨负极材料。
步骤A1所述的二苯二氯硅烷、KH572去离子水和1,3-双(氨丙烷基)四甲基二硅醚的用量比为2mmol:1mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、KH572和1,3-双(氨丙烷基)四甲基二硅醚质量和的1%,去离子水、四乙基氢氧化铵、异丙醇和KH560的质量比为10:0.21:32:40.25。
步骤A2所述的中间体1和环氧笼型聚倍半硅氧烷的摩尔比为8:1,改性剂、3,3,4,4-联苯四甲酸二酐和三乙胺的摩尔比为1:8:8.3。
步骤A3所述的聚酰胺酸盐、改性填料和去离子水的用量比为10g:2g:0.3g:200mL。
所述的改性填料由如下步骤制成:
步骤B1:将天然石墨、硝酸钠和浓硫酸混合均匀,在转速为150r/min,温度为0℃的条件下,搅拌并加入高锰酸钾,搅拌2h后,升温至35℃,加入去离子水,加入完毕后升温至95℃,搅拌30min,加入双氧水,继续搅拌1h,过滤去除滤液,制得预处理石墨;
步骤B2:将预处理石墨、聚乙烯吡咯烷酮和甲醇混合均匀,加入六水合硝酸锌和2-甲基咪唑,在转速为200r/min,温度为20℃的条件下,搅拌4h,过滤去除滤液,将底物在温度为800℃,氩气保护的条件下,保温4h后,在盐酸溶液中,浸泡10h,过滤洗涤至中性,制得改性石墨;
步骤B3:将草酸亚锡分散在去离子水中,加入柠檬酸溶液混合均匀,调pH为中性,加入改性石墨,在频率为20kHz的条件下,超声处理3h,过滤去除滤液,将底物在温度为400℃的条件下,保温2h,制得改性基体,将改性基体分散在乙醇中,在转速为200r/min,温度为50℃的条件下,搅拌并加入3-巯丙基三乙氧基硅烷和去离子水,进行反应1h,制得改性填料。
步骤B1所述的天然石墨、硝酸钠、浓硫酸、高锰酸钾、去离子水和双氧水的用量比为1g:0.5g:26mL:3g:46mL:10mL,双氧水质量分数为30%。
步骤B2所述的预处理石墨、聚乙烯吡咯烷酮、甲醇、六水合硝酸锌和2-甲基咪唑的用量比为40mg:50mg:40mL:0.73g:0.85g,盐酸溶液的浓度为2mol/L。
步骤B3所述的草酸亚锡、去离子水、柠檬酸溶液和改性石墨的用量比为1.2g:2.5mL:5mL:1g,3-巯丙基三乙氧基硅烷的用量为改性石墨质量的3%。
实施例2
一种高性能石墨负极材料制备工艺,具体包括如下步骤:
步骤A1:将二苯二氯硅烷、KH572和去离子水混合,在转速为200r/min,温度为65℃的条件下,搅拌13min后,加入浓硫酸和1,3-双(氨丙烷基)四甲基二硅醚,进行反应5h后,调节pH至中性,制得中间体1,将去离子水、四乙基氢氧化铵和异丙醇混合均匀,在转速为200r/min,温度为34℃的条件下,搅拌并加入KH560,搅拌5h后,升温至78℃,进行反应18h,过滤去除滤液,制得环氧笼型聚倍半硅氧烷;
步骤A2:将中间体1、环氧笼型聚倍半硅氧烷和DMF混合均匀,在转速为150r/min,温度为35℃,pH值为12的条件下,进行反应6h,减压蒸馏,制得改性剂,将改性剂、3,3,4,4-联苯四甲酸二酐和N,N-二甲基乙酰胺混合,在转速为300r/min,温度为2℃的条件下,搅拌3h,升温至25℃,加入三乙胺,继续反应3h后,将反应产物加入丙酮中,静置3h后,过滤去除滤液,制得聚酰胺酸盐;
步骤A3:将聚酰胺酸盐、改性填料、三乙胺和去离子水混合,在转速为500r/min,365nm紫外光照射的条件下,搅拌1.5h后,倒入模具中,在温度为零下196℃的条件下,保温20h,再在温度为零下15℃,真空度为3Pa的条件下,干燥10h,放入管式炉中,在温度为250℃的条件下,保温2h,升温至980℃,碳化处理4h,制得高性能石墨负极材料。
步骤A1所述的二苯二氯硅烷、KH572去离子水和1,3-双(氨丙烷基)四甲基二硅醚的用量比为2mmol:1mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、KH572和1,3-双(氨丙烷基)四甲基二硅醚质量和的1.3%,去离子水、四乙基氢氧化铵、异丙醇和KH560的质量比为10:0.21:32:40.25。
步骤A2所述的中间体1和环氧笼型聚倍半硅氧烷的摩尔比为8:1,改性剂、3,3,4,4-联苯四甲酸二酐和三乙胺的摩尔比为1:8:8.3。
步骤A3所述的聚酰胺酸盐、改性填料和去离子水的用量比为10g:2g:0.3g:200mL。
所述的改性填料由如下步骤制成:
步骤B1:将天然石墨、硝酸钠和浓硫酸混合均匀,在转速为200r/min,温度为2℃的条件下,搅拌并加入高锰酸钾,搅拌2h后,升温至40℃,加入去离子水,加入完毕后升温至95℃,搅拌35min,加入双氧水,继续搅拌1.3h,过滤去除滤液,制得预处理石墨;
步骤B2:将预处理石墨、聚乙烯吡咯烷酮和甲醇混合均匀,加入六水合硝酸锌和2-甲基咪唑,在转速为200r/min,温度为25℃的条件下,搅拌5h,过滤去除滤液,将底物在温度为830℃,氩气保护的条件下,保温5h后,在盐酸溶液中,浸泡13h,过滤洗涤至中性,制得改性石墨;
步骤B3:将草酸亚锡分散在去离子水中,加入柠檬酸溶液混合均匀,调pH为中性,加入改性石墨,在频率为25kHz的条件下,超声处理4h,过滤去除滤液,将底物在温度为430℃的条件下,保温2.5h,制得改性基体,将改性基体分散在乙醇中,在转速为200r/min,温度为55℃的条件下,搅拌并加入3-巯丙基三乙氧基硅烷和去离子水,进行反应1.3h,制得改性填料。
步骤B1所述的天然石墨、硝酸钠、浓硫酸、高锰酸钾、去离子水和双氧水的用量比为1g:0.5g:26mL:3g:46mL:10mL,双氧水质量分数为30%。
步骤B2所述的预处理石墨、聚乙烯吡咯烷酮、甲醇、六水合硝酸锌和2-甲基咪唑的用量比为40mg:50mg:40mL:0.73g:0.85g,盐酸溶液的浓度为2mol/L。
步骤B3所述的草酸亚锡、去离子水、柠檬酸溶液和改性石墨的用量比为1.2g:2.5mL:5mL:1g,3-巯丙基三乙氧基硅烷的用量为改性石墨质量的3%。
实施例3
一种高性能石墨负极材料制备工艺,具体包括如下步骤:
步骤A1:将二苯二氯硅烷、KH572和去离子水混合,在转速为300r/min,温度为70℃的条件下,搅拌15min后,加入浓硫酸和1,3-双(氨丙烷基)四甲基二硅醚,进行反应6h后,调节pH至中性,制得中间体1,将去离子水、四乙基氢氧化铵和异丙醇混合均匀,在转速为300r/min,温度为35℃的条件下,搅拌并加入KH560,搅拌6h后,升温至80℃,进行反应20h,过滤去除滤液,制得环氧笼型聚倍半硅氧烷;
步骤A2:将中间体1、环氧笼型聚倍半硅氧烷和DMF混合均匀,在转速为200r/min,温度为40℃,pH值为12的条件下,进行反应7h,减压蒸馏,制得改性剂,将改性剂、3,3,4,4-联苯四甲酸二酐和N,N-二甲基乙酰胺混合,在转速为500r/min,温度为3℃的条件下,搅拌4h,升温至25℃,加入三乙胺,继续反应4h后,将反应产物加入丙酮中,静置3h后,过滤去除滤液,制得聚酰胺酸盐;
步骤A3:将聚酰胺酸盐、改性填料、三乙胺和去离子水混合,在转速为800r/min,365nm紫外光照射的条件下,搅拌1.5h后,倒入模具中,在温度为零下196℃的条件下,保温25h,再在温度为零下15℃,真空度为3Pa的条件下,干燥15h,放入管式炉中,在温度为250℃的条件下,保温3h,升温至1000℃,碳化处理5h,制得高性能石墨负极材料。
步骤A1所述的二苯二氯硅烷、KH572去离子水和1,3-双(氨丙烷基)四甲基二硅醚的用量比为2mmol:1mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、KH572和1,3-双(氨丙烷基)四甲基二硅醚质量和的1.5%,去离子水、四乙基氢氧化铵、异丙醇和KH560的质量比为10:0.21:32:40.25。
步骤A2所述的中间体1和环氧笼型聚倍半硅氧烷的摩尔比为8:1,改性剂、3,3,4,4-联苯四甲酸二酐和三乙胺的摩尔比为1:8:8.3。
步骤A3所述的聚酰胺酸盐、改性填料和去离子水的用量比为10g:2g:0.3g:200mL。
所述的改性填料由如下步骤制成:
步骤B1:将天然石墨、硝酸钠和浓硫酸混合均匀,在转速为200r/min,温度为3℃的条件下,搅拌并加入高锰酸钾,搅拌3h后,升温至40℃,加入去离子水,加入完毕后升温至98℃,搅拌40min,加入双氧水,继续搅拌1.5h,过滤去除滤液,制得预处理石墨;
步骤B2:将预处理石墨、聚乙烯吡咯烷酮和甲醇混合均匀,加入六水合硝酸锌和2-甲基咪唑,在转速为300r/min,温度为25℃的条件下,搅拌6h,过滤去除滤液,将底物在温度为850℃,氩气保护的条件下,保温6h后,在盐酸溶液中,浸泡15h,过滤洗涤至中性,制得改性石墨;
步骤B3:将草酸亚锡分散在去离子水中,加入柠檬酸溶液混合均匀,调pH为中性,加入改性石墨,在频率为30kHz的条件下,超声处理5h,过滤去除滤液,将底物在温度为450℃的条件下,保温3h,制得改性基体,将改性基体分散在乙醇中,在转速为300r/min,温度为60℃的条件下,搅拌并加入3-巯丙基三乙氧基硅烷和去离子水,进行反应1.5h,制得改性填料。
步骤B1所述的天然石墨、硝酸钠、浓硫酸、高锰酸钾、去离子水和双氧水的用量比为1g:0.5g:26mL:3g:46mL:10mL,双氧水质量分数为30%。
步骤B2所述的预处理石墨、聚乙烯吡咯烷酮、甲醇、六水合硝酸锌和2-甲基咪唑的用量比为40mg:50mg:40mL:0.73g:0.85g,盐酸溶液的浓度为2mol/L。
步骤B3所述的草酸亚锡、去离子水、柠檬酸溶液和改性石墨的用量比为1.2g:2.5mL:5mL:1g,3-巯丙基三乙氧基硅烷的用量为改性石墨质量的3%。
对比例1
本对比例与实施例1相比用中间体1代替改性剂,其余步骤相同。
对比例2
本对比例与实施例1相比用苯二胺代替改性剂,其余步骤相同。
对比例3
本对比例与实施例1相比用预处理石墨代替改性石墨,其余步骤相同。
将实施例1-3和对比例1-3制得的负极材料、羧甲基纤维素、导电炭黑、丁苯橡胶按照95:1.5:1.5:2的质量比在去离子水中磁力搅拌8h,使其混合均匀。将混合得到的浆料涂布在铜箔上,60℃真空干燥后作为工作电极。采用金属锂作为对电极,隔膜为Celgard2325,电解液为1mol/L的LiPF6-EC(碳酸乙烯酯)/DMC(碳酸二甲酯)/EMC(碳酸甲乙酯)(体积比为1:1:1),在充满高纯氩气的手套箱中完成CR2016型扣式半电池组装,将组装好的扣式电池;
将电池试样以0.05C恒流放电至0.01V,所得容量记为0.05C充电容量;然后静置5min,以0.1C恒流充电至电压3.0V,所得容量记为0.1C放电容量;最后停止运行,首次库伦效率为0.05C充电容量/0.1C放电容量。
以0.1C恒流放电至0.01V,静置5min,然后以0.1C恒流充电至电压3.0V;接着静置5min,然后以0.1C恒流放电至0.01V,所得容量为0.1C对应的放电容量;最后停止运行,记录第二次放电容容量为0.1C对应的放电容量。
以0.2C恒流放电至0.01V,静置5min,然后以0.2C恒流充电至电压3.0V;接着静置5min,然后以0.2C恒流放电至0.01V,所得容量为0.2C对应的放电容量;最后停止运行,记录第二次放电容容量为0.2C对应的放电容量。
以0.2C恒流放电至0.01V,静置5min,然后以0.2C恒流充电至电压3.0V;以上依次循环500次和800次,记录放电容量,计算容量保持率,检测结果如下表所示;
由上表可知本申请具有很好的锂离子容量,且电池使用寿命长。
以上内容仅仅是对本发明的构思所作的举例和说明,所属本技术领域的技术人员对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
Claims (1)
1.一种高性能石墨负极材料制备工艺,其特征在于:具体包括如下步骤:
步骤A1:将二苯二氯硅烷、KH572和去离子水混合搅拌后,加入浓硫酸和1,3-双(氨丙烷基)四甲基二硅醚,进行反应后,调节pH至中性,制得中间体1,将去离子水、四乙基氢氧化铵和异丙醇混合搅拌并加入KH560,搅拌处理后,升温反应,过滤去除滤液,制得环氧笼型聚倍半硅氧烷;
步骤A2:将中间体1、环氧笼型聚倍半硅氧烷和DMF混合反应,减压蒸馏,制得改性剂,将改性剂、3,3,4,4-联苯四甲酸二酐和N,N-二甲基乙酰胺混合搅拌后,升温并加入三乙胺,继续反应,将反应产物加入丙酮中,静置处理,再过滤去除滤液,制得聚酰胺酸盐;
步骤A3:将聚酰胺酸盐、改性填料、三乙胺和去离子水在365nm紫外光照射下混合搅拌后,倒入模具中,冷冻干燥,升温保温,再碳化处理,制得高性能石墨负极材料;
步骤A1所述的将二苯二氯硅烷、KH572和去离子水混合搅拌后,加入浓硫酸和1,3-双(氨丙烷基)四甲基二硅醚,进行反应后,调节pH至中性,制得中间体1中的二苯二氯硅烷、KH572、去离子水和1,3-双(氨丙烷基)四甲基二硅醚的用量比为2mmol:1mmol:20mL:2mmol,浓硫酸的用量为二苯二氯硅烷、KH572和1,3-双(氨丙烷基)四甲基二硅醚质量和的1-1.5%,所述的将去离子水、四乙基氢氧化铵和异丙醇混合搅拌并加入KH560,搅拌处理后,升温反应,过滤去除滤液,制得环氧笼型聚倍半硅氧烷中的去离子水、四乙基氢氧化铵、异丙醇和KH560的质量比为10:0.21:32:40.25;
步骤A2所述的中间体1和环氧笼型聚倍半硅氧烷的摩尔比为8:1,改性剂、3,3,4,4-联苯四甲酸二酐和三乙胺的摩尔比为1:8:8.3;
所述的改性填料由如下步骤制成:
步骤B1:将天然石墨、硝酸钠和浓硫酸混合搅拌并加入高锰酸钾,搅拌处理后,升温并加入去离子水,加入完毕后继续升温,搅拌处理,加入双氧水,继续搅拌,过滤去除滤液,制得预处理石墨;
步骤B2:将预处理石墨、聚乙烯吡咯烷酮和甲醇混合均匀,加入六水合硝酸锌和2-甲基咪唑,搅拌处理,过滤去除滤液,将底物保温处理后,在盐酸溶液中浸泡,过滤洗涤至中性,制得改性石墨;
步骤B3:将草酸亚锡分散在去离子水中,加入柠檬酸溶液混合均匀,调pH为中性,加入改性石墨,超声处理,过滤去除滤液,将底物保温处理,制得改性基体,将改性基体分散在乙醇中,搅拌并加入3-巯丙基三乙氧基硅烷和去离子水,进行反应,制得改性填料;
步骤B1所述的天然石墨、硝酸钠、浓硫酸、高锰酸钾、去离子水和双氧水的用量比为1g:0.5g:26mL:3g:46mL:10mL;
步骤B2所述的预处理石墨、聚乙烯吡咯烷酮、甲醇、六水合硝酸锌和2-甲基咪唑的用量比为40mg:50mg:40mL:0.73g:0.85g;
步骤B3所述的草酸亚锡、去离子水、柠檬酸溶液和改性石墨的用量比为1.2g:2.5mL:5mL:1g,3-巯丙基三乙氧基硅烷的用量为改性石墨质量的3%。
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