CN113258046B - 一种锂/钠离子电池负极材料及其制备方法 - Google Patents
一种锂/钠离子电池负极材料及其制备方法 Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000007773 negative electrode material Substances 0.000 title claims description 23
- 239000013081 microcrystal Substances 0.000 claims abstract description 22
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 21
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000018417 cysteine Nutrition 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 16
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000010406 cathode material Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 239000002114 nanocomposite Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-YPZZEJLDSA-N carbon-10 atom Chemical group [10C] OKTJSMMVPCPJKN-YPZZEJLDSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 4
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- 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
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
本发明公开了一种锂/钠离子电池负极材料及其制备方法,该负极材料由以下重量份的原料制备所得:CMK‑8 20~30份、NiSe2八面体微晶3~7份、类石墨烯二硫化钼10~20份、碳纳米管3~6份、半胱氨酸5~10份。本发明以CMK‑8为模板,在其表面附着由类石墨烯二硫化钼、NiSe2八面体微晶、碳纳米管构成的立体结构,内载丰富的通道,易于锂/钠离子在通道中迁移穿梭,嵌入与脱出,大大提高锂/钠离子的充放电比容量,同时其内部大量的空间可以有效的避免负极材料的体积膨胀,并可以对锂/钠离子的快速嵌入和脱出起到缓冲调节作用,延长负极材料的使用寿命。
Description
技术领域
本发明涉及电池材料制备领域,具体涉及一种锂/钠离子电池负极材料及其制备方法。
背景技术
人类对全球能源供应的持续关注在一定程度上刺激了具有可循环充放电、高容量、长循环寿命及低成本等优点的能源储备技术的发展。锂/钠离子电池因其具有能量密度高、自放电流小、安全性高、可大电流充放电、循环次数多、寿命长等优点,已广泛应用于手机、笔记本电脑、数码相机、电动汽车、航空航天、军事装备等多个领域。
负极材料是锂/钠离子电池的重要组成部分,其性能严重制约着锂/钠离子电池的性能。目前,现有的锂/钠离子负极材料普遍存在导电性较差,在锂/钠离子脱嵌过程中缓冲材料体积急剧变化而无法保证其结构和电化学稳定性的缺陷。
发明内容
为解决上述问题,本发明提供了一种锂/钠离子电池负极材料及其制备方法。
为实现上述目的,本发明采取的技术方案为:
锂/钠离子电池负极材料,该负极材料由CMK-8、NiSe2八面体微晶、类石墨烯二硫化钼、碳纳米管、半胱氨酸制备所得。
进一步地,该负极材料由以下重量份的原料制备所得:
CMK-8 20~30份、NiSe2八面体微晶3~7份、类石墨烯二硫化钼10~20份、碳纳米管3~6份、半胱氨酸5~10份。
优选地,该负极材料由以下重量份的原料制备所得:
CMK-8 20份、NiSe2八面体微晶3份、类石墨烯二硫化钼10份、碳纳米管3份、半胱氨酸5份。
优选地,该负极材料由以下重量份的原料制备所得:
CMK-8 30份、NiSe2八面体微晶7份、类石墨烯二硫化钼20份、碳纳米管6份、半胱氨酸10份。
优选地,该负极材料由以下重量份的原料制备所得:
CMK-8 25份、NiSe2八面体微晶5份、类石墨烯二硫化钼15份、碳纳米管4.5份、半胱氨酸7.5份。
本发明还提供了一种锂/钠离子电池负极材料的制备方法,包括如下步骤:
S1、按上述的配方称取各组分;
S2、将称取的CMK-8超声分散于水中,形成CMK-8悬浊液;
S3、搅拌状态下,向CMK-8悬浊液中加入类石墨烯二硫化钼,待吸附完全后,加入NiSe2八面体微晶和半胱氨酸,反应完全后,加入碳纳米管,60~100W超声处理2~5h,烘干,在氮气气氛下,800~900℃煅烧3~4h,充分研磨,干燥,即得。
本发明具有以下有益效果:
以CMK-8为模板,在其表面附着由类石墨烯二硫化钼、NiSe2八面体微晶、碳纳米管构成的立体结构,内载丰富的通道,易于锂/钠离子在通道中迁移穿梭,嵌入与脱出,大大提高锂/钠离子的充放电比容量,同时其内部大量的空间可以有效的避免负极材料的体积膨胀,并可以对锂/钠离子的快速嵌入和脱出起到缓冲调节作用,延长负极材料的使用寿命。
具体实施方式
为了使本发明的目的及优点更加清楚明白,以下结合实施例对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
实施例1
锂/钠离子电池负极材料,通过以下方法制备所得:
S1、按重量份称取:CMK-8 20份、NiSe2八面体微晶3份、类石墨烯二硫化钼10份、碳纳米管3份、半胱氨酸5份;
S2、将称取的CMK-8超声分散于水中,形成CMK-8悬浊液;
S3、搅拌状态下,向CMK-8悬浊液中加入类石墨烯二硫化钼,待吸附完全后,加入NiSe2八面体微晶和半胱氨酸,反应完全后,加入碳纳米管,60~100W超声处理2~5h,烘干,在氮气气氛下,800~900℃煅烧3~4h,充分研磨,干燥,即得。
实施例2
锂/钠离子电池负极材料,通过以下方法制备所得:
S1、按重量份称取:CMK-8 30份、NiSe2八面体微晶7份、类石墨烯二硫化钼20份、碳纳米管6份、半胱氨酸10份;
S2、将称取的CMK-8超声分散于水中,形成CMK-8悬浊液;
S3、搅拌状态下,向CMK-8悬浊液中加入类石墨烯二硫化钼,待吸附完全后,加入NiSe2八面体微晶和半胱氨酸,反应完全后,加入碳纳米管,60~100W超声处理2~5h,烘干,在氮气气氛下,800~900℃煅烧3~4h,充分研磨,干燥,即得。
实施例3
锂/钠离子电池负极材料,通过以下方法制备所得:
S1、按重量份称取:CMK-8 25份、NiSe2八面体微晶5份、类石墨烯二硫化钼15份、碳纳米管4.5份、半胱氨酸7.5份;
S2、将称取的CMK-8超声分散于水中,形成CMK-8悬浊液;
S3、搅拌状态下,向CMK-8悬浊液中加入类石墨烯二硫化钼,待吸附完全后,加入NiSe2八面体微晶和半胱氨酸,反应完全后,加入碳纳米管,60~100W超声处理2~5h,烘干,在氮气气氛下,800~900℃煅烧3~4h,充分研磨,干燥,即得。
将实施例1制备得到的负极材料: 乙炔黑:海藻酸钠按质量比7:1:1的比例在混合后,充分研磨,以水为溶剂,调成浆料,均匀涂覆至铜箔上,转移至真空烘箱中80℃烘干12h,用冲片机制备直径为15mm的电极片,获得电池负极,在充满氩气气氛的手套箱内组装电池,以锂片作为正极,以Cellgard2300多孔膜作为隔膜,以1mol/L的LiPF6+DMC(体积比1:1)混合溶液作为 电解质,组装扣式电池。
在25℃下,以0.1A/g的倍率在0.1-3V间进行充放电循环时,其首次充放电比容量为593.1mAh/g、591.7 mAh/g、592.3 mAh/g;充放电循环500次的放电容量0.5C为573.7mAh/g、567.8 mAh/g、568.7 mAh/g该结果表明本发明的电极材料具有较高的容量和优异的循环稳定性,是高能量密度长寿命锂离子电池的潜在应用电极。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以作出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (4)
1.锂/钠离子电池负极材料,其特征在于,该负极材料由CMK-8 20~30份、NiSe2八面体微晶3~7份、类石墨烯二硫化钼10~20份、碳纳米管3~6份、半胱氨酸5~10份制备所得;
上述锂/钠离子电池负极材料的制备方法,包括如下步骤:
S1、按上述配方称取各组分;
S2、将称取的CMK-8超声分散于水中,形成CMK-8悬浊液;
S3、搅拌状态下,向CMK-8悬浊液中加入类石墨烯二硫化钼,待吸附完全后,加入NiSe2八面体微晶和半胱氨酸,反应完全后,加入碳纳米管,60~100W超声处理2~5h,烘干,在氮气气氛下,800~900℃煅烧3~4h,充分研磨,干燥,即得。
2.如权利要求1所述的锂/钠离子电池负极材料,其特征在于,该负极材料由以下重量份的原料制备所得:
CMK-8 20份、NiSe2八面体微晶3份、类石墨烯二硫化钼10份、碳纳米管3份、半胱氨酸5份。
3.如权利要求1所述的锂/钠离子电池负极材料,其特征在于,该负极材料由以下重量份的原料制备所得:
CMK-8 30份、NiSe2八面体微晶7份、类石墨烯二硫化钼20份、碳纳米管6份、半胱氨酸10份。
4.如权利要求1所述的锂/钠离子电池负极材料,其特征在于,该负极材料由以下重量份的原料制备所得:
CMK-8 25份、NiSe2八面体微晶5份、类石墨烯二硫化钼15份、碳纳米管4.5份、半胱氨酸7.5份。
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