CN113991082B - 一种硅灰制备锂离子电池硅碳负极材料的方法 - Google Patents
一种硅灰制备锂离子电池硅碳负极材料的方法 Download PDFInfo
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- 229910021487 silica fume Inorganic materials 0.000 title claims abstract description 127
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
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- 238000000034 method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
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- 229910021430 silicon nanotube Inorganic materials 0.000 description 2
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- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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Abstract
本发明涉及一种硅灰制备锂离子电池硅碳负极材料的方法。本发明将硅灰置于酸性溶液中浸泡预处理,硅灰和碳材料混合均匀得到硅灰/碳混合材料,将金属催化剂加入到硅灰/碳混合材料中球磨得到硅灰/碳/金属催化剂混合粉;将硅灰/碳/金属催化剂混合粉或与添加剂混合均匀后压制成片,焙烧得到硅灰/碳/金属催化剂复合材料粉体或硅灰/碳/金属催化剂复合材料;将硅灰/碳/金属催化剂复合材料粉体或硅灰/碳/金属催化剂复合材料制备成电极作为阴极,石墨为阳极,在熔盐电解质体系内恒电压电解得到电解阴极,清洗除去熔盐电解质即得具有纳米硅合金结构的硅碳负极材料,或去除硅碳负极材料中的金属化合物得到具有纳米多孔硅结构的硅碳负极材料。
Description
技术领域
本发明涉及一种硅灰制备锂离子电池硅碳负极材料的方法,属于能源材料技术领域。
背景技术
由于石墨负极材料容量有限,发展下一代高容量锂离子电池负极材料是目前研究的重点。在众多潜在的锂离子电池负极材料中,具备4200mA h g-1理论容量的硅材料被认为最有希望取代石墨材料。此外硅材料还具备合适的放电电压且储量丰富(地壳中含量第二高),具有潜在的低成本、环保、无毒的潜力。然而,硅材料的体积膨胀和较差的本征电子导电性等问题会以协同方式加速硅基电极的坍塌和容量衰减,致使目前硅材料在锂电负极材料上的应用仍然较为有限。通过减小硅颗粒的尺寸、引入多孔结构、纳米线结构、与碳材料进行有效包覆等有助于释放硅体积膨胀应力,防止在锂插入过程中硅的开裂。与块体材料相比,相关纳米碳复合材料能够有效地适应体积变化,极大缩短电子传输和锂离子扩散的距离,显著提高了锂离子电池硅基负极的循环寿命。但具备硅纳米结构硅碳材料的制备往往涉及到复杂的制备工艺、高昂的成本。
发明内容
针对锂离子电池硅基负极材料存在的技术问题,本发明提供了一种硅灰制备锂离子电池硅碳负极材料的方法,即采用硅灰、碳材料和金属催化剂为原料,经熔盐电解可控制备具备多种纳米硅结构的硅碳复合电极材料,硅碳复合电极材料作为锂离子电池硅碳负极材料具有优异的电化学性能。
硅灰又称作微硅粉,在工业中被列为固体废弃物,作为工业冶炼的副产品,微灰主要由电弧炉冶炼工业硅或硅铁合金所产生,当硅石被碳质还原剂还原成金属时会释放出一氧化硅蒸汽,烟气在炉的上部氧化和冷凝并产生无定形二氧化硅微球,即硅灰。由于硅灰形成过程中几乎与杂质同时形核,导致大多杂质主要以被包裹在硅灰颗粒内部的形式存在,故难以直接生产出高纯的二氧化硅产品;本发明将纳微米球形的硅灰直接制备成低成本的硅纳米结构材料并应用于高附加值的锂电硅碳负极材料上,不仅可以有效解决硅碳负极材料的高成本问题,同时解决了固废硅灰易产生的环境污染和资源浪费等问题。
一种硅灰制备锂离子电池硅碳负极材料的方法,具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于酸性溶液中并在搅拌条件下浸泡预处理1~300min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;
(2)将步骤(1)硅灰和碳材料混合均匀得到硅灰/碳混合材料,将金属催化剂加入到硅灰/碳混合材料中,在不同气体氛围下球磨1~600min得到硅灰/碳/金属催化剂混合粉;
(3)将步骤(2)硅灰/碳/金属催化剂混合粉或与添加剂混合均匀后压制成片,在温度为400~1200℃、保护气或空气氛围下焙烧0.5~10h得到硅/碳/金属催化剂复合材料粉体或硅/碳/金属催化剂复合材料;其中添加剂为粘结剂和/或造孔剂;
(4)将步骤(3)硅/碳/金属催化剂复合材料粉体或硅灰/碳/金属催化剂复合材料制备的电极作为阴极,石墨为阳极,在保护气体氛围下的熔盐电解质体系内恒电压电解0.5~20h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的硅碳负极材料,或采用酸性溶液去除硅碳负极材料中的金属化合物得到具有纳米多孔硅结构的硅碳负极材料;
所述步骤(1)酸性溶液与硅灰的液固比mL:g不小于3:1,浸泡预处理的温度为20~100℃;
所述步骤(1)酸性溶液为HCl、H2SO4、HNO3、HF中的一种或多种,酸性溶液的浓度为0.01~10mol/L;
所述步骤(2)硅灰和碳材料的质量比为0.01~100:1,碳材料为葡萄糖、果糖、蔗糖、木糖、山梨糖、柠檬酸、淀粉、聚乙烯、聚丙烯、纤维素、石墨、石墨烯、氧化石墨烯、碳纳米管、芳香烃、芳香族脂类、石油沥青或煤沥青;金属催化剂为金属或金属的氧化物,金属为Ca、K、Na、Mg、Al、Ni、Cu、Ag、Ti、Li、Fe或Sn;
进一步的,所述步骤(2)金属催化剂占硅灰/碳/金属催化剂混合粉质量的0.1%~50%;
所述步骤(3)粘结剂为PMMA、PVP、PEG或PVA,造孔剂为淀粉、碳酸氢铵、尿素、CaO或CaCl2;
所述步骤(3)添加剂的加入量为硅灰/碳/金属催化剂混合粉的0.1~10wt.%;
所述步骤(2)和步骤(3)的保护气为氮气或氩气;
所述步骤(4)熔盐电解质为SrCl2、MgCl2、CaCl2、AlCl3、LiCl、NaCl、KCl中的一种或多种,保护气体为氮气、氩气或二氧化碳,恒电压为1.0~3.0V;
所述步骤(4)酸性溶液为HCl、H2SO4、HNO3、HF中的一种或多种,酸性溶液的浓度为0.01~10mol/L。
本发明的有益效果是:
(1)本发明基于硅灰利用熔盐电解方法在低温条件下即可实现具备多种纳米硅结构、碳层有效包覆的硅碳负极材料制备,通过金属催化剂可控制备不同类型纳米硅结构,碳材料以骨架支撑作用可有效阻碍熔盐电解过程中硅纳米结构的塌陷;
(2)本发明硅纳米结构和碳层包覆可极大缓解硅材料在充放电过程中体积膨胀和电导率差的问题,可以显著提高其作为硅基负极材料的电化学性能;
(3)本发明原料丰富、价格低廉、操作容易且易放大,通过控制金属化合物的留存可以得到具有不同纳米硅结构的锂离子电池硅碳复合电极材料并表现出了优异的电化学性能;
(4)本发明将纳微米球形的硅灰直接制备成低成本的硅纳米结构材料并应用于高附加值的锂电硅碳负极材料上,有效解决了固废硅灰易产生的环境污染和资源浪费等问题。
附图说明
图1为本发明工艺流程图;
图2为实施例1所得纳米多孔硅/Ag/C复合材料作为负极时的锂离子电池性能测试结果;
图3为实施例2所得纳米多孔硅-Cu/C复合材料作为负极时的锂离子电池性能测试结果;
图4为实施例3所得纳米多孔硅-Al/C复合材料作为负极时的锂离子电池性能测试结果;
图5为实施例4所得纳米多孔硅/C复合材料作为负极时的锂离子电池性能测试结果;
图6为实施例5所得硅纳米线-Ni/C复合材料作为负极时的锂离子电池性能测试结果。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:一种硅灰制备锂离子电池硅碳负极材料的方法(见图1),具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于酸性溶液(浓度为2mol/L的HCl溶液)中并在温度为20℃、搅拌条件下浸泡预处理60min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;其中酸性溶液与硅灰的液固比mL:g为10:1;
(2)将步骤(1)硅灰和碳材料(人造石墨)混合均匀得到硅灰/石墨混合材料,将金属催化剂(Ag粉)加入到硅灰/石墨混合材料中,在氩气氛围下球磨60min得到硅灰/石墨/Ag混合粉;其中硅灰和碳材料(人造石墨)的质量比为1:1,金属催化剂(Ag粉)占硅灰/石墨/Ag混合粉质量的0.1%;球磨转速为1500r/min;
(3)将步骤(2)硅灰/石墨/Ag混合粉置于温度为600℃、氮气氛围下焙烧1h得到硅/石墨/Ag复合材料粉体;
(4)将步骤(3)硅/石墨/Ag复合材料粉体装置于接有石墨棒导线的自制石墨多孔容器中形成接触电极并作为阴极放在装有氯化锶熔盐电解质的石墨坩埚中,石墨坩埚充当阳极,在二氧化碳气体氛围下的熔盐电解质体系内恒电压电解20h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的纳米多孔硅-Ag/C复合材料;其中恒电压电解的温度为150℃,电压为3.5V;
(5)将步骤(4)的纳米多孔硅-Ag/C复合材料与导电剂炭黑、海藻酸钠粘结剂按70:15:15的质量比制备的电极片在手套箱中以锂片为对电极组装电池,在1A/g电流密度下进行充放电测试;
纳米多孔硅-Ag/C复合材料作为锂电负极制备的电池性能结果如图2所示,首次放电容量高达1646mAh/g,首次库伦效率可达到83.9%,经过200次循环后的可逆容量仍然保持1065mAh/g,容量保持率高达64.7%,具有较为优异的电池性能。
实施例2:一种硅灰制备锂离子电池硅碳负极材料的方法(见图1),具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于酸性溶液(浓度为0.01mol/L的HF溶液)中并在温度为40℃、搅拌条件下浸泡预处理30min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;其中酸性溶液与硅灰的液固比mL:g为15:1;
(2)将步骤(1)硅灰和碳材料(碳纳米管)混合均匀得到硅灰/碳纳米管混合材料,将金属催化剂(CuO粉)加入到硅灰/碳纳米管混合材料中,在空气氛围下球磨120min得到硅灰/碳纳米管/CuO混合粉;其中硅灰和碳材料(碳纳米管)的质量比为1:0.3,金属催化剂(CuO粉)占硅灰/碳纳米管/CuO混合粉质量的10%;球磨转速为300r/min;
(3)将步骤(2)硅灰/碳纳米管/CuO混合粉置于温度为800℃、空气氛围下焙烧2h得到硅/碳纳米管/CuO复合材料粉体;
(4)将步骤(3)硅/碳纳米管/CuO复合材料粉体装置于接有碳纳米管棒导线的自制石墨多孔容器中形成接触电极并作为阴极放在装有氯化锂熔盐电解质的石墨坩埚中,石墨坩埚充当阳极,在氩气氛围下的熔盐电解质体系内恒电压电解8h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的纳米多孔硅-Cu/C复合材料;其中恒电压电解的温度为650℃,电压为1.5V;
(5)将步骤(4)的纳米多孔硅-Cu/C复合材料与导电剂炭黑、海藻酸钠粘结剂按70:15:15的质量比制备的电极片在手套箱中以锂片为对电极组装电池,在1A/g电流密度下进行充放电测试;
纳米多孔硅/Cu/C复合材料作为锂电负极制备的电池性能结果如图3所示,首次放电容量高达2337mAh/g,首次库伦效率可达到83.6%,经过200次循环后的可逆容量仍然保持943mAh/g,容量保持率40.4%,具有较为优异的电池性能。
实施例3:一种硅灰制备锂离子电池硅碳负极材料的方法(见图1),具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于酸性溶液(浓度为3mol/L的HNO3溶液)中并在温度为40℃、搅拌条件下浸泡预处理300min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;其中酸性溶液与硅灰的液固比mL:g为5:1;
(2)将步骤(1)硅灰和碳材料(石油沥青)混合均匀得到硅灰/沥青混合材料,将金属催化剂(Al粉)加入到硅灰/沥青混合材料中,在氩气氛围下球磨300min得到硅灰/沥青/Al混合粉;其中硅灰和碳材料(沥青)的质量比为1:0.4,金属催化剂(Al粉)占硅灰/沥青/Al混合粉质量的10%;球磨转速为1000r/min;
(3)将步骤(2)硅灰/沥青/Al混合粉置于温度为300℃、氩气氛围下焙烧5h得到硅/沥青/Al复合材料粉体;
(4)将步骤(3)硅/沥青/Al复合材料粉体装置于接有石墨棒导线的自制石墨多孔容器中形成接触电极并作为阴极放在装有氯化锂熔盐电解质的石墨坩埚中,石墨坩埚充当阳极,在氩气氛围下的熔盐电解质体系内恒电压电解12h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的纳米多孔硅-Al/C复合材料;其中恒电压电解的温度为250℃,电压为2.5V;
(5)将步骤(4)的纳米多孔硅-Al/C复合材料与导电剂炭黑、海藻酸钠粘结剂按70:15:15的质量比制备的电极片在手套箱中以锂片为对电极组装电池,在1A/g电流密度下进行充放电测试;
纳米多孔硅-Al/C复合材料作为锂电负极制备的电池性能结果如图4所示,首次放电容量高达2027mAh/g,首次库伦效率可达到87.4%,经过200次循环后的可逆容量仍然保持1172mAh/g,容量保持率高达57.8%,具有较为优异的电池性能。
实施例4:一种硅灰制备锂离子电池硅碳负极材料的方法(见图1),具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于酸性溶液(浓度为6mol/L的H2SO4溶液)中并在温度为60℃、搅拌条件下浸泡预处理120min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;其中酸性溶液与硅灰的液固比mL:g为8:1;
(2)将步骤(1)硅灰、碳材料(葡萄糖)和水混合均匀形成浆料,浆料烘干得到硅灰/葡萄糖混合材料,将金属催化剂(Mg粉)加入到硅灰/葡萄糖混合材料中,在氩气氛围下球磨100min得到硅灰/葡萄糖/Mg混合粉;其中硅灰和碳材料(葡萄糖)的质量比为1:1.5,金属催化剂(Mg粉)占硅灰/葡萄糖/Mg混合粉质量的20%;球磨转速为500r/min;
(3)将步骤(2)硅灰/葡萄糖/Mg混合粉与淀粉、PMMA研磨均匀后压制成片,压片压力为1MPa,保压时间为10min,然后置于温度为400℃、氮气氛围下焙烧2h得到硅/葡萄糖/Mg复合材料;其中淀粉的加入量为硅灰/葡萄糖/Mg混合粉的0.5wt.%,PMMA的加入量为硅灰/葡萄糖/Mg混合粉的1wt.%;
(4)将步骤(3)硅/葡萄糖/Mg复合材料固定在钼棒导线上形成接触电极并作为阴极置于装有氯化镁熔盐电解质的石墨坩埚中,石墨坩埚直接充当阳极,在氩气氛围下的熔盐电解质体系内恒电压电解5h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的纳米多孔硅-Mg/C复合材料;其中恒电压电解的温度为750℃,电压为2.0V,采用浓度为2mol/L的HCl溶液除去残留镁化合物得到了纳米多孔硅/C复合材料;
(5)将步骤(4)的纳米多孔硅/C复合材料与导电剂炭黑、海藻酸钠粘结剂按70:15:15的质量比制备的电极片在手套箱中以锂片为对电极组装电池,在1A/g电流密度下进行充放电测试;
纳米多孔硅/C复合材料作为锂电负极制备的电池性能结果如图5所示,首次放电容量高达1459mAh/g,首次库伦效率可达到77.3%,经过200次循环后的可逆容量仍然保持1135mAh/g,容量保持率高达77.8%,具有较为优异的电池性能。
实施例5:一种硅灰制备锂离子电池硅碳负极材料的方法(见图1),具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于酸性溶液(浓度为0.2mol/L的HF溶液)中并在温度为80℃、搅拌条件下浸泡预处理60min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;其中酸性溶液与硅灰的液固比mL:g为20:1;
(2)将步骤(1)硅灰、碳材料(氧化石墨烯)和水混合均匀形成浆料,浆料烘干得到硅灰/氧化石墨烯混合材料,将金属催化剂(Ni粉)加入到硅灰/氧化石墨烯混合材料中,在氩气氛围下球磨150min得到硅灰/氧化石墨烯/Ni混合粉;其中硅灰和碳材料(氧化石墨烯)的质量比为1:0.5,金属催化剂(Ni粉)占硅灰/氧化石墨烯/Ni混合粉质量的10%;球磨转速为800r/min;
(3)将步骤(2)硅灰/氧化石墨烯/Ni混合粉与PVP研磨均匀并在空气氛围中热压成片,热压温度为1000℃,压片压力为10MPa,保压时间为100min得到硅灰/氧化石墨烯
/NiO复合材料;其中PVP的加入量为硅灰/氧化石墨烯/Ni混合粉的1wt.%;
(4)将步骤(3)硅灰/氧化石墨烯/NiO复合材料固定在钼棒导线上形成接触电极并作为阴极置于装有氯化钙熔盐电解质的石墨坩埚中,石墨坩埚直接充当阳极,在氩气氛围下的熔盐电解质体系内恒电压电解6h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的硅纳米线-Ni/C复合材料;其中恒电压电解的温度为800℃,电压为2.0V;
(5)将步骤(4)的硅纳米线-Ni/C复合材料与导电剂炭黑、海藻酸钠粘结剂按70:15:15的质量比制备的电极片在手套箱中以锂片为对电极组装电池,在1A/g电流密度下进行充放电测试;
硅纳米线-Ni/C复合材料作为锂电负极制备的电池性能结果如图6所示,首次放电容量高达1786mAh/g,首次库伦效率可达到86.8%,经过200次循环后的可逆容量仍然保持965mAh/g,容量保持率高达54.0%,而且随着循环次数的增加电池容量开始有上升趋势,具有较为优异的电池性能。
以上结合附图对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本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。
Claims (1)
1.一种硅灰制备锂离子电池硅碳负极材料的方法,其特征在于,具体步骤如下:
(1)将硅灰经去离子水清洗,然后置于浓度为0.2mol/L的HF溶液中,在温度为80℃、搅拌条件下浸泡预处理60min,去离子水洗涤至洗涤液为中性,固液分离并烘干得到预处理硅灰;其中HF溶液与硅灰的液固比为20mL:1g;
(2)将步骤(1)预处理硅灰、氧化石墨烯和水混合均匀形成浆料,浆料烘干得到硅灰/氧化石墨烯混合材料,将Ni粉加入到硅灰/氧化石墨烯混合材料中,在氩气氛围下球磨150min得到硅灰/氧化石墨烯/Ni混合粉;其中硅灰和氧化石墨烯的质量比为1:0.5,Ni粉占硅灰/氧化石墨烯/Ni混合粉质量的10%;球磨转速为800r/min;
(3)将步骤(2)硅灰/氧化石墨烯/Ni混合粉与PVP研磨均匀并在空气氛围中热压成片,热压温度为1000℃,压片压力为10MPa,保压时间为100min得到硅灰/氧化石墨烯/NiO复合材料;其中PVP的加入量为硅灰/氧化石墨烯/Ni混合粉的1wt.%;
(4)将步骤(3)硅灰/氧化石墨烯/NiO复合材料固定在钼棒导线上形成接触电极并作为阴极置于装有氯化钙熔盐电解质的石墨坩埚中,石墨坩埚直接充当阳极,在氩气氛围下的熔盐电解质体系内恒电压电解6h得到电解阴极,电解阴极冷却后清洗除去熔盐电解质即得具有纳米硅合金结构的硅纳米线-Ni/C复合材料;其中恒电压电解的温度为800℃,电压为2.0V。
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