CN107068987A - 一种锂离子电池负极片的制作方法及锂离子电池 - Google Patents
一种锂离子电池负极片的制作方法及锂离子电池 Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002153 silicon-carbon composite material Substances 0.000 claims abstract description 17
- 239000004966 Carbon aerogel Substances 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims abstract description 12
- 238000005253 cladding Methods 0.000 claims abstract description 10
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 230000004888 barrier function Effects 0.000 claims abstract description 8
- 238000004804 winding Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000005174 2,4-dihydroxybenzoic acids Chemical class 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 12
- 229910021487 silica fume Inorganic materials 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 6
- 238000000605 extraction Methods 0.000 claims description 6
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000000352 supercritical drying Methods 0.000 claims description 5
- 229940114055 beta-resorcylic acid Drugs 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 2
- 239000012190 activator Substances 0.000 claims description 2
- 239000005030 aluminium foil Substances 0.000 claims description 2
- 239000007767 bonding agent Substances 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
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- 239000000126 substance Substances 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 description 1
- -1 Sugar alcohol fatty acid ester Chemical class 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 238000000465 moulding Methods 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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Abstract
本发明提供一种锂离子电池负极片的制作方法,本发明提供的锂离子电池负极片的制作方法所制作的负极片比表面积大、体积变化可控且化学稳定性高。本发明还提供一种锂离子电池,包括正极片、隔膜、电解液、外壳及本发明提供的锂离子电池负极片的制作方法所制作的负极片;所述正极片、负极片及隔膜卷绕后装入所述外壳,经注电解液、封口后组成所述锂离子电池。本发明提供的锂离子电池,包括碳气凝胶包覆的硅碳复合材料的负极,锂离子电池的内阻小、倍率性能好、循环寿命长且能量密度高。
Description
【技术领域】
本发明涉及锂离子电池技术领域,尤其涉及一种锂离子电池负极片的制作方法及锂离子电池。
【背景技术】
负极是锂离子电池的重要组成部分,由于碳基材料比表面积大、导电性好、成本低、空隙率大、电极制备简单等优点,成为了应用最广泛的电极材料。目前,锂离子电池主要应用的负极材料为石墨,石墨材料的理论容量372mAh/g,实际应用已达到370mAh/g,因此,石墨电极本身较低的理论储锂容量使其很难再取得突破性进展,严重制约了高能量密度动力电池的发展。
硅具有较高的理论容量(4200mAh/g)和较低的脱锂电位(<0.5V),成为最有潜力取代石墨的锂离子电池负极材料,然而,由硅作为活性材料制得的负极在充放电后硅晶格体积膨胀达到了360%,导致了硅颗粒粉化、负极活性物质与导电剂接触差、固体电解质膜重复生长而消耗电解液及锂源及循环性能差的问题。
鉴于此,实有必要提供一种新型的锂离子电池负极片的制作方法及锂离子电池以克服以上缺陷。
【发明内容】
本发明的目的是提供一种能够限制硅晶格体积膨胀的锂离子电池负极片的制作方法,并且提供一种锂离子电池,包括本发明的锂离子电池负极片的制作方法所制得的负极片,本发明提供的锂离子电池具有内阻小、倍率性能好、循环寿命长和能量密度高的特点。
为了实现上述目的,本发明提供一种锂离子电池负极片的制作方法,包括如下步骤:
步骤一:按摩尔比为1:0.5称取2,4-二羟基苯甲酸和K2CO3,同时加入一定量的去离子水并搅拌,直至2,4-二羟基苯甲酸与K2CO3完全反应,得到澄清溶液;
步骤二:在步骤一所得的澄清溶液中加入一定量的甲醛和K2CO3,将反应仪器密封,在室温下反应5-7h,得到淡黄色溶液;
步骤三:在步骤二所得的淡黄色溶液中加入一定量的表面活化剂溶液及去离子水,同时加入一定量的纳米硅粉,在室温下,以300-500rpm的转速搅拌,进行溶胶-凝胶反应,反应时间为3d,制得反应产物;
步骤四:将步骤三所得的反应产物取出,离心分离,用丙酮溶液洗涤除去残留的表面活性剂,再用丙酮萃取1d;
步骤五:将步骤四萃取得到的产物放入密封系统中,加入适量的石油醚作为超临界干燥的置换介质,在惰性气体保护下以5-10℃/min升温至250℃,保持温度在250℃、系统压力7MPa以上干燥90min;
步骤六:将步骤五干燥后的产物送入卧式电炉中,在惰性气体保护下以3-5℃/min升温至900-1200℃进行炭化,得到碳气凝胶包覆的硅碳复合材料;
步骤七:将步骤六所得到的硅碳复合材料与导电剂、粘结剂、溶剂混合成浆涂于铜箔上得到锂离子电池负极片。
本发明提供的锂离子电池负极片的制作方法所制作的负极片比表面积大、体积变化可控且化学稳定性高。
本发明还提供一种锂离子电池,包括正极片、隔膜、电解液、外壳及本发明提供的锂离子电池负极片的制作方法所制作的负极片;所述正极片、负极片及隔膜卷绕后装入所述外壳,经注电解液、封口后组成所述锂离子电池。
本发明提供的锂离子电池,包括碳气凝胶包覆的硅碳复合材料的负极,锂离子电池的内阻小、倍率性能好、循环寿命长且能量密度高。
【附图说明】
图1为本发明实施例1所制备的碳气凝胶的SEM图;
图2为本发明提供的碳气凝胶的成型机理图;
图3为本发明实施例1、实施例2及实施例3所制备的锂离子电池的3C循环图。
【具体实施方式】
为了使本发明的目的、技术方案和有益技术效果更加清晰明白,以下结合附图和具体实施方式,对本发明进行进一步详细说明。应当理解的是,本说明书中描述的具体实施方式仅仅是为了解释本发明,并不是为了限定本发明。
本发明提供一种锂离子电池负极片的制作方法,包括如下步骤:
步骤一:按摩尔比为1:0.5称取2,4-二羟基苯甲酸和K2CO3,同时加入一定量的去离子水并搅拌,直至2,4-二羟基苯甲酸与K2CO3完全反应,得到澄清溶液;
步骤二:在步骤一所得的澄清溶液中加入一定量的甲醛和K2CO3,将反应仪器密封,在室温下反应5-7h(小时),得到淡黄色溶液;
步骤三:在步骤二所得的淡黄色溶液中加入一定量的表面活化剂溶液及去离子水,同时加入一定量的纳米硅粉,在室温下,以300-500rpm(转/分)的转速搅拌,进行溶胶-凝胶反应,反应时间为3d(天),制得反应产物;
步骤四:将步骤三所得的反应产物取出,离心分离,用丙酮溶液洗涤除去残留的表面活性剂,再用丙酮萃取1d;
步骤五:将步骤四萃取得到的产物放入密封系统中,加入适量的石油醚作为超临界干燥的置换介质,在惰性气体保护下以5-10℃/min升温至250℃,保持温度在250℃、系统压力7MPa以上干燥90min;
步骤六:将步骤五干燥后的产物送入卧式电炉中,在惰性气体保护下以3-5℃/min升温至900-1200℃进行炭化,得到碳气凝胶包覆的硅碳复合材料;
步骤七:将步骤六所得到的硅碳复合材料与导电剂、粘结剂、溶剂混合成浆涂于铜箔上得到锂离子电池负极片。
具体的,所述步骤一中加入去离子水后,2,4-二羟基苯甲酸的摩尔浓度为0.8-1.2mol/L。
具体的,所述步骤二中的甲醛与2,4-二羟基苯甲酸的摩尔比为2:1。
具体的,所述步骤二中的K2CO3与2,4-二羟基苯甲酸的摩尔比为0.01:1。
具体的,所述步骤三中的表面活化剂溶液为SPAN80(司盘80,化学成分是失水山梨糖醇脂肪酸酯)和环己烷按照1:50的体积比配制形成。
具体的,所述步骤三中加入的去离子水与表面活化剂溶液的体积比为1:(3-4)。
具体的,所述步骤三中加入的纳米硅粉与2,4-二羟基苯甲酸的摩尔比为(0.5-1):1。
具体的,所述步骤六中惰性气体的流量为200-500mL/min。
本发明提供的锂离子电池负极片的制作方法,以2,4-二羟基苯甲酸和甲醛为有机溶胶-凝胶的前驱体,以纳米硅粉为核、SPAN80和环己烷为表面活性剂制备了包覆纳米硅粉的有机溶胶-凝胶,使用超临界干燥法对有机溶胶-凝胶产物进行干燥,保持了原有的多孔网络结构,从而得到高空隙率、超低密度的有机溶胶-凝胶,再经高温炭化的到最终产物:碳气凝胶包覆的硅碳复合材料。
如图1及图2所示,碳气凝胶作为一种纳米网络多孔材料,其网络之间相互交联,纳米硅粉很好的锁合在网络结构之中,在充放电过程中,锂离子由纳米孔道嵌入,与纳米硅粉进行结合,提高了硅碳复合材料的比容量;同时,由于纳米硅粉颗粒被碳气凝胶网络锁合住,在充放电过程中,碳骨架对纳米粉有一个缓冲作用,抑制住了硅由于体积效应而发生粉化。
本发明提供的锂离子电池负极片的制作方法所制作的负极片比表面积大、体积变化可控且化学稳定性高。
本发明还提供一种锂离子电池,包括正极片、隔膜、电解液、外壳及由上述的锂离子电池负极片的制作方法所制作的负极片;所述正极片、负极片及隔膜卷绕后装入所述外壳,经注电解液、封口后组成所述锂离子电池。
具体的,所述正极片为正极活性物质与粘结剂、导电剂、溶剂混合成浆涂于铝箔上得到,所述正极活性物质为LiCoO2、LiMn2O4、LiFePO4、LiCo1-x-yNixMnyO2中的一种或几种,其中,x、y、x+y均小于1。
本发明提供的锂离子电池,包括碳气凝胶包覆的硅碳复合材料的负极,锂离子电池的内阻小、倍率性能好、循环寿命长且能量密度高。
实施例1:
1、称取1mol 2,4-二羟基苯甲酸和0.5mol K2CO3,同时加入1L的去离子水,搅拌,使2,4-二羟基苯甲酸与K2CO3发生中和反应,直至溶液变澄清,完全反应变成盐;
2、在澄清溶液中加入2mol甲醛和0.01mol K2CO3,将反应仪器密封,在室温下反应7h,溶液由无色变成淡黄色;
3、在淡黄色溶液中加入3L的由SPAN80和环己烷(按照1:50的体积比配制)表面活化剂溶液,同时加入0.6mol的纳米硅粉,在室温下,以400rpm的转速搅拌反应,进行溶胶-凝胶反应3d;
4、将反应产物取出,离心分离,用丙酮溶液洗涤除去残留的表面活性剂,再用丙酮萃取1d;
5、将萃取得到的产物放入密封系统中,加入适量的石油醚作为超临界干燥的置换介质,在惰性气体保护下以5℃/min升温至250℃,保持温度在250℃,系统压力7MPa以上干燥90min;
6、将干燥后的产物送入卧式电炉中在惰性气体保护下(流量为300mL/min)以5℃/min升温至1000℃进行炭化,得到碳气凝胶包覆的硅碳复合材料;
7、以所制得的硅碳复合材料为负极活性物质与导电剂、粘结剂、溶剂混合成浆涂于铜箔上得到负极片;以LiFePO4为正极活性物质与粘结剂、导电剂、溶剂混合成浆涂于铝箔上得到正极片;正、负极片与隔膜、电解液、外壳组成锂离子电池。
实施例2:
1、称取0.5mol 2,4-二羟基苯甲酸和0.25mol K2CO3,同时加入0.5L的去离子水,搅拌,使2,4-二羟基苯甲酸与K2CO3发生中和反应,直至溶液变澄清,完全反应变成盐;
2、在澄清溶液中加入1mol甲醛和0.005mol K2CO3,将反应仪器密封,在室温下反应5h,溶液由无色变成淡黄色;
3、在淡黄色溶液中加入1.5L的由SPAN80和环己烷(按照1:50的体积比配制)表面活化剂溶液,同时加入0.4mol的纳米硅粉,在室温下,以500rpm的转速搅拌反应,进行溶胶-凝胶反应3d;
4、将反应产物取出,离心分离,用丙酮溶液洗涤除去残留的表面活性剂,再用丙酮萃取1d;
5、将萃取得到的产物放入密封系统中,加入适量的石油醚作为超临界干燥的置换介质,在惰性气体保护下以10℃/min升温至250℃,保持温度在250℃,系统压力7MPa以上干燥90min;
6、将干燥后的产物送入卧式电炉中在惰性气体保护下(流量为400mL/min)以3℃/min升温至1000℃进行炭化,得到碳气凝胶包覆的硅碳复合材料;
7、以所制得的硅碳复合材料为负极活性物质与导电剂、粘结剂、溶剂混合成浆涂于铜箔上得到负极片;以LiFePO4为正极活性物质与粘结剂、导电剂、溶剂混合成浆涂于铝箔上得到正极片;正、负极片与隔膜、电解液、外壳组成锂离子电池。
实施例3:
1、称取0.8mol 2,4-二羟基苯甲酸和0.4mol K2CO3,同时加入1L的去离子水,搅拌,使2,4-二羟基苯甲酸与K2CO3发生中和反应,直至溶液变澄清,完全反应变成盐;
2、在澄清溶液中加入1.6mol甲醛和0.008mol K2CO3,将反应仪器密封,在室温下反应6h,溶液由无色变成淡黄色;
3、在淡黄色溶液中加入3L的由SPAN80和环己烷(按照1:50的体积比配制)表面活化剂溶液,同时加入0.8mol的纳米硅粉,在室温下,以300rpm的转速搅拌反应,进行溶胶-凝胶反应3d;
4、将反应产物取出,离心分离,用丙酮溶液洗涤除去残留的表面活性剂,再用丙酮萃取1d;
5、将萃取得到的产物放入密封系统中,加入适量的石油醚作为超临界干燥的置换介质,在惰性气体保护下以5℃/min升温至250℃,保持温度在250℃,系统压力7MPa以上干燥90min;
6、将干燥后的产物送入卧式电炉中在惰性气体保护下(流量为350mL/min)以4℃/min升温至1000℃进行炭化,得到碳气凝胶包覆的硅碳复合材料;
7、以所制得的硅碳复合材料为负极活性物质与导电剂、粘结剂、溶剂混合成浆涂于铜箔上得到负极片;以LiFePO4为正极活性物质与粘结剂、导电剂、溶剂混合成浆涂于铝箔上得到正极片;正、负极片与隔膜、电解液、外壳组成锂离子电池。
本发明各实施例所制备的负极片在不同的循环次数后厚度膨胀率如下表1所示。
表1:不同循环次数后负极片厚度膨胀率
由表1可以看出,本发明实施例所制备的负极片,在循环20次时,膨胀率仍低于130%,与现有的硅碳材料的体积膨胀率360%相比,大大降低了硅晶格的体积膨胀率,作为负极材料的性能良好。
图3为本发明实施例1、实施例2及实施例3所制备的锂离子电池的3C循环图。由图3可以看出,本发明提供的锂离子电池的循环性能良好,在3C条件下,200次循环的容量保持率在90%以上。
本发明并不仅仅限于说明书和实施方式中所描述,因此对于熟悉领域的人员而言可容易地实现另外的优点和修改,故在不背离权利要求及等同范围所限定的一般概念的精神和范围的情况下,本发明并不限于特定的细节、代表性的设备和这里示出与描述的图示示例。
Claims (10)
1.一种锂离子电池负极片的制作方法,其特征在于:包括如下步骤:
步骤一:按摩尔比为1:0.5称取2,4-二羟基苯甲酸和K2CO3,同时加入一定量的去离子水并搅拌,直至2,4-二羟基苯甲酸与K2CO3完全反应,得到澄清溶液;
步骤二:在步骤一所得的澄清溶液中加入一定量的甲醛和K2CO3,将反应仪器密封,在室温下反应5-7h,得到淡黄色溶液;
步骤三:在步骤二所得的淡黄色溶液中加入一定量的表面活化剂溶液及去离子水,同时加入一定量的纳米硅粉,在室温下,以300-500rpm的转速搅拌,进行溶胶-凝胶反应,反应时间为3d,制得反应产物;
步骤四:将步骤三所得的反应产物取出,离心分离,用丙酮溶液洗涤除去残留的表面活性剂,再用丙酮萃取1d;
步骤五:将步骤四萃取得到的产物放入密封系统中,加入适量的石油醚作为超临界干燥的置换介质,在惰性气体保护下以5-10℃/min升温至250℃,保持温度在250℃、系统压力7MPa以上干燥90min;
步骤六:将步骤五干燥后的产物送入卧式电炉中,在惰性气体保护下以3-5℃/min升温至900-1200℃进行炭化,得到碳气凝胶包覆的硅碳复合材料;
步骤七:将步骤六所得到的硅碳复合材料与导电剂、粘结剂、溶剂混合成浆涂于铜箔上得到锂离子电池负极片。
2.如权利要求1所述的锂离子电池负极片的制作方法,其特征在于:所述步骤一中加入去离子水后,2,4-二羟基苯甲酸的摩尔浓度为0.8-1.2mol/L。
3.如权利要求2所述的锂离子电池负极片的制作方法,其特征在于:所述步骤二中的甲醛与2,4-二羟基苯甲酸的摩尔比为2:1。
4.如权利要求3所述的锂离子电池负极片的制作方法,其特征在于:所述步骤二中的K2CO3与2,4-二羟基苯甲酸的摩尔比为0.01:1。
5.如权利要求4所述的锂离子电池负极片的制作方法,其特征在于:所述步骤三中的表面活化剂溶液为SPAN80和环己烷按照1:50的体积比配制形成。
6.如权利要求5所述的锂离子电池负极片的制作方法,其特征在于:所述步骤三中加入的去离子水与表面活化剂溶液的体积比为1:(3-4)。
7.如权利要求6所述的锂离子电池负极片的制作方法,其特征在于:所述步骤三中加入的纳米硅粉与2,4-二羟基苯甲酸的摩尔比为(0.5-1):1。
8.如权利要求7所述的锂离子电池负极片的制作方法,其特征在于:所述步骤六中惰性气体的流量为200-500mL/min。
9.一种锂离子电池,其特征在于:包括正极片、隔膜、电解液、外壳及如权利要求1至8任意一项所述的锂离子电池负极片的制作方法所制作的负极片;所述正极片、负极片及隔膜卷绕后装入所述外壳,经注电解液、封口后组成所述锂离子电池。
10.如权利要求9所述的锂离子电池,其特征在于:所述正极片为正极活性物质与粘结剂、导电剂、溶剂混合成浆涂于铝箔上得到,所述正极活性物质为LiCoO2、LiMn2O4、LiFePO4、LiCo1-x-yNixMnyO2中的一种或几种,其中,x、y、x+y均小于1。
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CN111587501A (zh) * | 2018-12-18 | 2020-08-25 | 三星Sdi株式会社 | 用于可再充电锂电池的正极活性材料、包括其的正极和可再充电锂电池 |
CN111725501A (zh) * | 2020-06-30 | 2020-09-29 | 山东大学 | 硫钼锌/碳纳米片结构复合材料及其制备方法与作为负极材料的应用 |
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CN111587501A (zh) * | 2018-12-18 | 2020-08-25 | 三星Sdi株式会社 | 用于可再充电锂电池的正极活性材料、包括其的正极和可再充电锂电池 |
CN111587501B (zh) * | 2018-12-18 | 2024-01-16 | 三星Sdi株式会社 | 用于可再充电锂电池的正极活性材料、包括其的正极和可再充电锂电池 |
CN111725501A (zh) * | 2020-06-30 | 2020-09-29 | 山东大学 | 硫钼锌/碳纳米片结构复合材料及其制备方法与作为负极材料的应用 |
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