CN114229829B - 基于碳纳米片的钠离子电池负极材料及其制备方法和应用 - Google Patents
基于碳纳米片的钠离子电池负极材料及其制备方法和应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 65
- 239000002135 nanosheet Substances 0.000 title claims abstract description 39
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 30
- 239000010405 anode material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000002064 nanoplatelet Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 14
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000001630 malic acid Substances 0.000 claims description 14
- 235000011090 malic acid Nutrition 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 13
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000007790 solid phase Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000002055 nanoplate Substances 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000007773 negative electrode material Substances 0.000 description 12
- 239000003575 carbonaceous material Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 230000001351 cycling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
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Abstract
本发明属于钠离子电池技术领域,公开了基于碳纳米片的钠离子电池负极材料及其制备方法和应用,该钠离子电池负极材料为氧化石墨烯@CeO2/碳纳米片。本发明制备的先通过在碳纳米片上附着CeO2;再通过氧化石墨烯包裹外层;使CeO2处于碳纳米片和氧化石墨烯的中间,增加了材料的稳定性,氧化石墨烯进一步改善了负极材料的导电性能。
Description
技术领域
本发明属于钠离子电池技术领域,具体涉及基于碳纳米片的钠离子电池负极材料及其制备方法和应用。
背景技术
随着电动车产业以及可再生能源(如风能、太阳能等)在世界范围内的快速发展,大规模的能源储存技术已经成为制约其可持续发展的关键,也是未来解决风能及太阳能等可再生能源不连续性与能源需求连续性矛盾的主要途径。钠离子电池具有资源丰富、成本低廉、能量转换效率高、循环寿命长、维护费用低、安全性高等诸多优势,能够满足新能源电池领域高性价比和高安全性等的应用要求。
近几年钠离子电池的研究相继取得重要的进展,其中负极材料的研究主要集中于碳材料以及一些非碳材料(金属及氧化物材料、合金材料及磷等)。非碳材料对锂和钠都表现出高的存储容量,但是由于导电率低、体积变化大和易粉化等问题,即便在商业化程度很高的锂离子电池中仍未获得大规模应用,而碳基材料不仅具有较低的嵌钠平台,较高的容量和良好的循环稳定性,还具有资源丰富,制备简单等优点。因此,碳材料是最有希望推动钠离子产业化的关键负极材料,但现有的碳材料稳定性仍然不够好,比容量比较低不能满足钠离子电池长久的使用。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此,本发明提出一种基于碳纳米片的钠离子电池负极材料及其制备方法和应用,该钠离子电池负极材料的稳定性和比容量高。
为实现上述目的,本发明采用以下技术方案:
一种钠离子电池负极材料,所述钠离子电池负极材料为氧化石墨烯@CeO2/碳纳米片。
优选地,所述氧化石墨烯@CeO2/碳纳米片的导电率为4.8×10-3-7.5×10-3。
一种钠离子电池负极材料的制备方法,包括以下步骤:
将碳纳米片和溶剂混合,再加入粘结剂和CeO2搅拌反应,水浴反应,固液分离,取固相得到碳纳米片/CeO2复合材料;
将所述碳纳米片/CeO2复合材料加入氧化石墨烯溶液中搅拌,固液分离,取固相煅烧,得到所述钠离子电池负极材料氧化石墨烯@CeO2/碳纳米片。
优选地,所述碳纳米片的具体制备过程为:将碳源进行煅烧,冷却至室温后,再将所述碳源搅拌分散在有机酸溶液中,固液分离,取固相洗涤至中性,干燥,得到碳纳米片。
进一步优选地,所述煅烧分为两次煅烧,第一次煅烧的温度为100~200℃,第一次煅烧的时间为1~2h,第一次煅烧的气氛为空气气氛;第二次煅烧的温度为500~700℃,第二次煅烧的时间为4~6h,第二次煅烧的气氛为Ar。
进一步优选地,所述碳源为柠檬酸和苹果酸中的至少一种。
进一步优选地,所述有机酸为醋酸、柠檬酸、草酸和苹果酸中的至少一种。
优选地,所述CeO2的具体制备过程为:向氯化铈溶液中加入碳酸氢铵溶液,反应,溶液pH达7时停止加入碳酸氢铵,搅拌,过滤,醇洗沉淀至中性,干燥,焙烧,再通过X射线照射,制得CeO2。
其中,CeO2具有优异的氧化还原能力,从而二氧化铈晶格中容易形成氧空位,通过X射线照射,增加了CeO2的氧空位。
进一步优选地,所述氯化铈的浓度为0.5~2mol/L。
进一步优选地,所述碳酸氢铵的浓度为0.5~2mol/L。
优选地,所述溶剂为乙醇、去离子水中的一种。
优选地,所述搅拌反应的时间为2-4h。
优选地,所述水浴反应的温度为60~80℃,水浴反应的时间为2~4h。
优选地,所述粘结剂为葡萄糖。
葡萄糖既可以充当粘结剂又可以充当碳源。
优选地,所述碳纳米片和CeO2的质量比为(5~10):1。
优选地,所述氧化石墨烯和碳纳米片/CeO2的质量比为1:(2~5)。
本发明还提供一种电池,包括所述的钠离子电池负极材料。
优选地,所述电池的比容量为780-870mAh/g。
相对于现有技术,本发明的有益效果如下:
1、本发明先通过在碳纳米片上附着CeO2;其中,碳纳米片不仅是CeO2的附着位点,还能改善负极材料的导电性,为负极材料膨胀提供缓存空间;再通过氧化石墨烯包裹外层;使CeO2处于碳纳米片和氧化石墨烯的中间,增加了材料的稳定性,氧化石墨烯进一步改善了负极材料的导电性能。
2、本发明的碳源为柠檬酸和苹果酸,在加热的条件下会产生CO2,在此过程中会增加碳纳米片的孔体积,为CeO2提供更多的附着点,提高负极材料的比容量。CeO2具有优异的氧化还原能力,通过X射线照射,增加了CeO2的氧空位;氧空位的增加,提高了负极材料的稳定性和比容量。
附图说明
图1为本发明实施例1制得的氧化石墨烯@CeO2/碳纳米片的SEM图;
图2为本发明实施例1制得的氧化石墨烯@CeO2/碳纳米片的XRD图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述,以充分地理解本发明的目的、特征和效果。显然,所描述的实施例只是本发明的一部分实施例,而不是全部实施例,基于本发明的实施例,本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例,均属于本发明保护的范围。
实施例1
本实施例的钠离子电池负极材料制备的方法,包括以下步骤:
(1)将柠檬酸放入坩埚中,先置于100℃Ar气氛下煅烧1h,再置于500℃Ar气氛下煅烧4h,冷却至室温后,再将其分散在醋酸溶液中并搅拌2h,过滤并用去离子水冲洗至中性,在60℃干燥2h后,得到碳纳米片;
(2)取0.5mol/L碳酸氢铵溶液加入50mL 0.5mol/L氯化铈溶液,反应温度60℃,溶液pH值达7时停止加入碳酸氢铵,继续搅拌1h,然后过滤,醇洗沉淀至中性,80℃下干燥3h,500℃下焙烧2h,再通过X射线照射2h,制得CeO2;
(3)将5g步骤(1)的碳纳米片加入到乙醇溶液中,加入葡萄糖和1g步骤(2)中的CeO2搅拌反应2h后,再将溶液在60℃的水浴中并反应2h,过滤并用去离子水冲洗至中性,在60℃下干燥得到碳纳米片/CeO2复合材料;
(4)将1mol氧化石墨烯,加入到去离子水中,在常温条件下搅拌1h,得到溶液A,将2mol步骤(3)的碳纳米片/CeO2复合材料加入到溶液中,搅拌2h,过滤干燥,置于800℃Ar气氛下煅烧4h,得到钠离子电池负极材料氧化石墨烯@CeO2/碳纳米片。
实施例2
本实施例的钠离子电池负极材料制备的方法,包括以下具体步骤:
(1)将苹果酸放入坩埚中,先置于Ar气氛和120℃下煅烧1.2h,再置于Ar气氛和550℃下煅烧4.5h,冷却至室温后,再将其分散在醋酸溶液中并搅拌3h,过滤并用去离子水冲洗至中性,在60℃干燥3h后,得到碳纳米片;
(2)取1mol/L碳酸氢铵溶液加入50mL1mol/L氯化铈溶液,反应温度60℃,溶液pH达7时停止加入碳酸氢铵,继续搅拌1h,然后过滤,醇洗沉淀至中性,80℃下干燥3h,500℃下焙烧2h,再通过X射线照射2h,制得CeO2;
(3)将6g步骤(1)的碳纳米片加入到乙醇溶液中,再加入葡萄糖和1g步骤(2)中的CeO2搅拌反应2h后,再将溶液在60℃的水浴中并反应2h,过滤并用去离子水冲洗至中性,在60℃下干燥得到碳纳米片/CeO2复合材料;
(4)将1mol氧化石墨烯,加入到去离子水中,在常温条件下搅拌1h,得到溶液A,将3mol步骤(3)的碳纳米片/CeO2复合材料加入到溶液中,搅拌2.5h,过滤干燥,置于Ar气氛和820℃下煅烧4.5h,得到钠离子电池负极材料氧化石墨烯@CeO2/碳纳米片。
实施例3
本实施例的钠离子电池负极材料制备的方法,包括以下具体步骤:
(1)将苹果酸放入坩埚中,先置于Ar气氛和150℃下煅烧1.5h,再置于Ar气氛和600℃下煅烧5h,冷却至室温后,将苹果酸分散在草酸溶液中并搅拌5h,过滤并用去离子水冲洗至中性。在60℃干燥5h后,得到碳纳米片;
(2)取1.5mol/L碳酸氢铵溶液加入50mL1.5mol/L氯化铈溶液,反应温度60℃,溶液pH值达7时停止加入碳酸氢铵,继续搅拌1h,然后过滤,醇洗沉淀至中性,80℃下干燥3h,500℃下焙烧2h,再通过X射线照射2h,制得CeO2;
(3)将8g步骤(1)的碳纳米片加入到乙醇溶液中,再加入葡萄糖和1g步骤(2)中的CeO2搅拌反应2h后,再将溶液在60℃的水浴中并反应2h,过滤并用去离子水冲洗至中性,在60℃下干燥得到碳纳米片/CeO2复合材料;
(4)将1mol氧化石墨烯,加入到去离子水中,在常温条件下搅拌1.5h,得到溶液A,将4mol步骤(3)的碳纳米片/CeO2复合材料加入到溶液中,搅拌3h,过滤干燥,置于Ar气氛和850℃下煅烧5h,得到钠离子电池负极材料氧化石墨烯@CeO2/碳纳米片。
实施例4
本实施例的钠离子电池负极材料制备的方法,包括以下具体步骤:
(1)将苹果酸放入坩埚中,先置于Ar气氛和200℃下煅烧2h,再置于700℃Ar气氛下煅烧6h,冷却至室温后,再将苹果酸分散在草酸溶液中并搅拌6h,过滤并用去离子水冲洗至中性,在60℃干燥6h后,得到碳纳米片;
(2)取2mol/L碳酸氢铵溶液加入50mL2mol/L氯化铈溶液,反应温度60℃,溶液pH达7时停止加入碳酸氢铵,继续搅拌1h,然后过滤,醇洗沉淀至中性,80℃下干燥3h,500℃下焙烧2h,再通过X射线照射2h,制得CeO2;
(3)将10g步骤(1)的碳纳米片加入到乙醇溶液中,再加入葡萄糖和1g步骤(2)中的CeO2搅拌反应2h后,再将溶液在60℃的水浴中并反应2h,过滤并用去离子水冲洗至中性,在60℃下干燥得到碳纳米片/CeO2复合材料;
(4)将1mol氧化石墨烯,加入到去离子水中,在常温条件下搅拌2h,得到溶液A,将5mol步骤(3)的碳纳米片/CeO2复合材料加入到溶液中,搅拌4h,过滤干燥,置于Ar气氛和900℃下煅烧6h,得到钠离子电池负极材料氧化石墨烯@CeO2/碳纳米片。
实施例5
本实施例与实施例4相比,本实施例的步骤(2)的CeO2不通过X射线照射。
对比例1
本对比例的钠离子电池负极材料制备的方法,包括以下具体步骤:
(1)将苹果酸放入坩埚中,先置于Ar气氛和200℃下煅烧2h,再置于700℃Ar气氛下煅烧6h,冷却至室温后,再将苹果酸分散在草酸溶液中并搅拌6h,过滤并用去离子水冲洗至中性,在60℃干燥6h后,得到碳纳米片;
(2)将1mol氧化石墨烯,加入到去离子水中,在常温条件下搅拌2h,得到溶液A,将5mol步骤(1)的碳纳米片加入到溶液中,搅拌4h,过滤干燥,置于Ar气氛和900℃下煅烧6h,得到钠离子电池负极材料氧化石墨烯@碳纳米片。
实施例1-5与对比例1、碳纳米片分析:
表1:实施例1-5与对比例1制得的钠离子电池效果数据
图1为本发明实施例1制得的氧化石墨烯@CeO2/碳纳米片的SEM图;从图1可以看出,负极材料孔径丰富,有利于锂的嵌入,同时给体积膨胀提供了缓和的空间。
图2为本发明实施例1制得的氧化石墨烯@CeO2/碳纳米片的XRD图;从图2可以得到CeO2已经成功的负载到了氧化石墨烯上,出现了CeO2的峰。
上面结合附图对本发明实施例作了详细说明,但是本发明不限于上述实施例,在所属技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。此外,在不冲突的情况下,本发明的实施例及实施例中的特征可以相互组合。
Claims (4)
1.一种钠离子电池负极材料的制备方法,其特征在于,包括以下步骤:
将碳纳米片和溶剂混合,再加入粘结剂、CeO2搅拌反应,水浴反应,固液分离,取固相,得到碳纳米片/ CeO2复合材料;
将所述碳纳米片/ CeO2复合材料加入氧化石墨烯溶液中搅拌,固液分离,取固相煅烧,得到所述钠离子电池负极材料;
其中,所述碳纳米片的具体制备过程为:将碳源进行煅烧,冷却,再将所述碳源搅拌分散在有机酸溶液中,固液分离,取固相洗涤至中性,干燥,得到碳纳米片;
所述煅烧分为两次煅烧,第一次煅烧的温度为100~200℃,第一次煅烧的时间为1~2 h,第一次煅烧的气氛为Ar;第二次煅烧的温度为500~700℃,第二次煅烧的时间为4~6 h,第二次煅烧的气氛为Ar;
所述碳源为柠檬酸和苹果酸中的至少一种;
所述CeO2的具体制备过程为:向氯化铈溶液中加入碳酸氢铵溶液,反应,溶液pH达7时停止加入碳酸氢铵,搅拌,过滤,醇洗沉淀至中性,干燥,焙烧,再通过X射线照射,制得CeO2。
2.根据权利要求1所述的制备方法,其特征在于,所述有机酸为醋酸、柠檬酸、草酸和苹果酸中的至少一种。
3.根据权利要求1所述的制备方法,其特征在于,所述粘结剂为葡萄糖。
4.根据权利要求1所述的制备方法,其特征在于,所述碳纳米片和CeO2的质量比为(5~10):1;所述氧化石墨烯和碳纳米片/ CeO2的质量比为1:(2~5)。
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