CN116589280B - 一种石墨匣钵的制备方法 - Google Patents

一种石墨匣钵的制备方法 Download PDF

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CN116589280B
CN116589280B CN202310863367.5A CN202310863367A CN116589280B CN 116589280 B CN116589280 B CN 116589280B CN 202310863367 A CN202310863367 A CN 202310863367A CN 116589280 B CN116589280 B CN 116589280B
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何江
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Changsha Zhongci New Material Technology Co ltd
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Abstract

本发明公开了一种石墨匣钵的制备方法，属于匣钵生产技术领域，将石墨/碱式磷酸铈复合粉末、炭粉、粘结剂和速干剂混合，用无水乙醇作为润湿剂进行造粒后模压制备匣钵坯体，将匣钵坯体在1550‑1650℃和保护气体的氛围下保温烧结，制备出石墨匣钵；通过磷酸二氢铵和硝酸铈通过水热沉淀方式附着在石墨表面，有助于增加石墨颗粒表面粗糙度，有助于增加模压成型后匣钵坯体的强度；减少粘结剂可以减少气孔的出现，有助于增加石墨匣钵的密度和力学性能；磷酸铈熔融后能够填充石墨匣钵上的孔隙，有助于提高石墨匣钵的尺寸稳定性和耐腐蚀性，从而增加其抗热震性以增加使用寿命；速干剂可以保证混合颗粒的流动性，还可以起到催化结化的作用。

Description

一种石墨匣钵的制备方法
技术领域
本发明属于匣钵生产技术领域，具体涉及一种石墨匣钵的制备方法。
背景技术
负极材料在制造过程中需要使用匣钵作为治具，新能源电池中负极材料是比较重要的部件，它的性能直接影响到电池的性能和寿命。负极材料烧结用匣钵的要求非常高，要求密度高、碳含量高、灰分小和抗折抗压强度高，统工艺制备的堇青石质匣钵具有很多缺点，比如堇青石匣钵的气孔率高、体积密度小以及内部杂质含量高，易与锂电池中的活性物质在高温下发生化学反应，导致匣钵容易被腐蚀，进而导致锂电池电极材料被污染。
石墨匣钵的碳含量能够高达99.9%，由于石墨粉末润滑性较好，需要在混料过程中加入树脂类粘结剂，从而便于石墨匣钵坯体的成型。但是模压成型的树脂碳的微晶小且无序，树脂碳较难石墨化，石墨化不完全会导致石墨匣钵的如果粘结剂含量过高，还会使石墨匣钵产品的孔隙率增大，降低石墨匣钵的密度和强度。
发明内容
本发明的目的在于提供一种能够增加石墨匣钵产品密度的制备方法，解决石墨匣钵密度和强度低的问题。
本发明的目的可以通过以下技术方案实现：
一种石墨匣钵的制备方法，包括如下步骤：
步骤一：将磷酸二氢铵用去离子水溶解，得到质量分数为3%的磷酸二氢铵溶液；将硝酸铈六水合物用去离子水搅拌溶解，得到质量分数为6.5%的硝酸铈水溶液；
步骤二：将石墨粉末加入硝酸铈水溶液中并超声分散1-2h，然后在55-65℃和200-300r/min的搅拌条件下加入磷酸二氢铵溶液，加入完毕后在相同的条件下继续搅拌100-150min，用氨水调节pH值至10.5-11，得到混合液；
步骤三：将混合液转移至反应釜中，在160-165℃条件下保温10-12h，冷却，过滤，将截留的固体用无水乙醇洗涤2-3次，再用去离子水洗涤2-3次，干燥，粉碎，得到石墨/碱式磷酸铈复合粉末；
步骤四：将石墨/碱式磷酸铈复合粉末、炭粉、粘结剂和速干剂用混捏锅混合，然后施加无水乙醇作为润湿剂进行造粒，得到混合颗粒；
步骤五：将混合颗粒在20-22MPa的压力下模压成型制备出匣钵坯体，将匣钵坯体转移至烧结炉中，在1550-1650℃和保护气体的氛围下保温24-30h，按照3-5℃/min的速率降温至300℃，自然冷却，得到石墨匣钵。
进一步地，硝酸铈水溶液、石墨粉末和磷酸二氢铵溶液的用量比为104mL：25-30g：95mL。
进一步地，石墨/碱式磷酸铈复合粉末、炭粉、粘结剂和速干剂的用量比为60-80g：5-10g：4-6g：2-4g。
进一步地，粘结剂为硼酚醛树脂；
进一步地，速干剂为对硝基苯甲酸或间硝基苯甲酸。
进一步地，石墨粉末的粒径为50±5μm。
进一步地，混合颗粒的粒径为0.1±0.02mm。
进一步地，保护气体包括氮气，但不仅限于氮气。
本发明的有益效果：
本发明石墨匣钵的制备方法能够减少粘结剂的用量，通过磷酸二氢铵和硝酸铈通过水热沉淀方式附着在石墨表面，有助于增加石墨颗粒表面粗糙度，从而增加石墨颗粒的空间位阻，增加模压成型后匣钵坯体的强度，减少粘结剂可以减少气孔的出现，有助于增加石墨匣钵的密度和力学性能。
速干剂可以在造粒过程中防止混合颗粒结块，保证混合颗粒的流动性，便于模压成型。速干剂中的硝基可以有助于硼酚醛树脂在高温炭化过程中发生脱氢缩聚反应，起到催化结化的作用，有助于树脂碳石墨化。石墨表面的碱式磷酸铈在高温下脱水形成磷酸铈，磷酸铈熔融后能够填充石墨匣钵上的孔隙，从而进一步减少石墨匣钵的显气孔率和增加密度，有助于提高石墨匣钵的尺寸稳定性和耐腐蚀性，从而增加其抗热震性以增加使用寿命。
具体实施方式
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述，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作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
本实施例提供一种石墨匣钵，包括如下实施步骤：
步骤一：将磷酸二氢铵用去离子水溶解，得到质量分数为3%的磷酸二氢铵溶液；将硝酸铈六水合物用去离子水搅拌溶解，得到质量分数为6.5%的硝酸铈水溶液。
步骤二：将50kg粒径为50±5μm的石墨粉末加入208L硝酸铈水溶液中并超声分散1h，然后在55℃和200r/min的搅拌条件下缓慢加入190L磷酸二氢铵溶液，加入完毕后在相同的条件下继续搅拌100min，用氨水调节pH值至10.5，得到混合液。
步骤三：将混合液转移至反应釜中，在160℃条件下保温10h，冷却，过滤，将截留的固体用无水乙醇洗涤2次，再用去离子水洗涤2-3次，干燥，粉碎，得到石墨/碱式磷酸铈复合粉末。
步骤四：将30kg石墨/碱式磷酸铈复合粉末、2.5kg炭粉、2kg硼酚醛树脂和1kg间硝基苯甲酸用混捏锅混合，然后施加无水乙醇作为润湿剂进行造粒，得到粒径为0.1±0.02mm的混合颗粒。
步骤五：将混合颗粒在20MPa的压力下模压成型制备出匣钵坯体，将匣钵坯体转移至烧结炉中，在1550℃和氮气氛围下保温24h，按照3℃/min的速率降温至300℃，自然冷却，得到石墨匣钵。
实施例2
本实施例提供一种石墨匣钵，包括如下实施步骤：
步骤一：将磷酸二氢铵用去离子水溶解，得到质量分数为3%的磷酸二氢铵溶液；将硝酸铈六水合物用去离子水搅拌溶解，得到质量分数为6.5%的硝酸铈水溶液。
步骤二：将55kg粒径为50±5μm的石墨粉末加入208L硝酸铈水溶液中并超声分散1.5h，然后在60℃和250r/min的搅拌条件下缓慢加入190L磷酸二氢铵溶液，加入完毕后在相同的条件下继续搅拌125min，用氨水调节pH值至10.8，得到混合液。
步骤三：将混合液转移至反应釜中，在162℃条件下保温11h，冷却，过滤，将截留的固体用无水乙醇洗涤2次，再用去离子水洗涤2次，干燥，粉碎，得到石墨/碱式磷酸铈复合粉末。
步骤四：将35kg石墨/碱式磷酸铈复合粉末、3.8kg炭粉、2.5kg硼酚醛树脂和1.6kg对硝基苯甲酸用混捏锅混合，然后施加无水乙醇作为润湿剂进行造粒，得到粒径为0.1±0.02mm的混合颗粒。
步骤五：将混合颗粒在21MPa的压力下模压成型制备出匣钵坯体，将匣钵坯体转移至烧结炉中，在1600℃和氮气氛围下保温27h，按照4℃/min的速率降温至300℃，自然冷却，得到石墨匣钵。
实施例3
本实施例提供一种石墨匣钵，包括如下实施步骤：
步骤一：将磷酸二氢铵用去离子水溶解，得到质量分数为3%的磷酸二氢铵溶液；将硝酸铈六水合物用去离子水搅拌溶解，得到质量分数为6.5%的硝酸铈水溶液。
步骤二：将60kg粒径为50±5μm的石墨粉末加入208L硝酸铈水溶液中并超声分散2h，然后在65℃和300r/min的搅拌条件下缓慢加入190L磷酸二氢铵溶液，加入完毕后在相同的条件下继续搅拌150min，用氨水调节pH值至11，得到混合液。
步骤三：将混合液转移至反应釜中，在165℃条件下保温12h，冷却，过滤，将截留的固体用无水乙醇洗涤3次，再用去离子水洗涤3次，干燥，粉碎，得到石墨/碱式磷酸铈复合粉末。
步骤四：将40kg石墨/碱式磷酸铈复合粉末、5kg炭粉、3kg硼酚醛树脂和2kg对硝基苯甲酸/间硝基苯甲酸用混捏锅混合，然后施加无水乙醇作为润湿剂进行造粒，得到粒径为0.1±0.02mm的混合颗粒。
步骤五：将混合颗粒在22MPa的压力下模压成型制备出匣钵坯体，将匣钵坯体转移至烧结炉中，在1650℃和氮气氛围下保温30h，按照5℃/min的速率降温至300℃，自然冷却，得到石墨匣钵。
对比例1：在实施例3的基础上，直接使用石墨粉末替代石墨/碱式磷酸铈复合粉末，其余步骤保持不变，制备出石墨匣钵。
对比例2：在实施例3的基础上，不添加速干剂，其余步骤保持不变，制备出石墨匣钵。
对比例3：在实施例3的基础上，不添加速干剂，并将硼酚醛树脂的用量增加到5kg，其余步骤保持不变，制备出石墨匣钵。
对实施例1-实施例3和对比例1-对比例3进行性能测试，将不同石墨匣钵分别制成230mm×114mm×65mm的试样，根据GB/T2997-2015和GB/T3001-2017对不同试样进行显气孔率和抗折强度的测定，结果如表1所示：
。
由表1可以看出，实施例1-实施例3中试样具有更小的显气孔率和更高的抗折强度，说明石墨与碱式磷酸铈复合后能够增加石墨匣钵的抗折强度，通过对比例还可以看出减少粘结剂的用量能够减小显气孔率，使用速干剂也可以起到增加抗强度的作用。
需要说明的是，在本文中，诸如术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求及其等同物限定。

Claims (7)

1.一种石墨匣钵的制备方法，其特征在于，包括如下步骤：
步骤一：将石墨粉末加入硝酸铈水溶液中并超声分散1-2h，在55-65℃和200-300r/min的搅拌条件下加入磷酸二氢铵溶液并继续搅拌100-150min，用氨水调节pH值至10.5-11，得到混合液；
步骤二：将混合液在160-165℃条件下保温10-12h，冷却，过滤，用无水乙醇和去离子水洗涤，干燥，粉碎，得到石墨/碱式磷酸铈复合粉末；
步骤三：将石墨/碱式磷酸铈复合粉末、炭粉、粘结剂和速干剂混合，用无水乙醇作为润湿剂进行造粒，得到混合颗粒；
步骤四：将混合颗粒在20-22MPa的压力下模压制备匣钵坯体，将匣钵坯体在1550-1650℃和保护气体的氛围下保温24-30h，按照3-5℃/min的速率降温至300℃，自然冷却，得到石墨匣钵；
所述速干剂为对硝基苯甲酸或间硝基苯甲酸。
2.根据权利要求1所述的一种石墨匣钵的制备方法，其特征在于，步骤一中所述磷酸二氢铵溶液的质量分数为3%，硝酸铈水溶液的质量分数为6.5%。
3.根据权利要求1所述的一种石墨匣钵的制备方法，其特征在于，步骤一中所述硝酸铈水溶液、石墨粉末和磷酸二氢铵溶液的用量比为104mL：25-30g：95mL。
4.根据权利要求1所述的一种石墨匣钵的制备方法，其特征在于，步骤三中所述石墨/碱式磷酸铈复合粉末、炭粉、粘结剂和速干剂的用量比为60-80g：5-10g：4-6g：2-4g。
5.根据权利要求1所述的一种石墨匣钵的制备方法，其特征在于，所述粘结剂为硼酚醛树脂。
6.根据权利要求1所述的一种石墨匣钵的制备方法，其特征在于，所述混合颗粒的粒径为0.1±0.02mm。
7.根据权利要求1所述的一种石墨匣钵的制备方法，其特征在于，所述保护气体包括但不仅限于氮气。
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09201525A (ja) * 1996-01-26 1997-08-05 Sumitomo Electric Ind Ltd ダイヤモンド焼結体の製造方法
JP2004299944A (ja) * 2003-03-31 2004-10-28 Jfe Chemical Corp 黒鉛質粒子、その製造方法、リチウムイオン二次電池およびその負極材料
WO2008084675A1 (ja) * 2006-12-26 2008-07-17 Mitsubishi Chemical Corporation 非水系二次電池用複合黒鉛粒子、それを含有する負極材料、負極及び非水系二次電池
CN104310979A (zh) * 2014-10-22 2015-01-28 华文蔚 一种功能陶瓷粉体材料及其制备方法和应用
CN107056299A (zh) * 2017-04-21 2017-08-18 华东理工大学 一种新型生产高强度炭石墨材料的复合添加剂及该炭石墨材料的制备方法
WO2017206299A1 (zh) * 2016-06-03 2017-12-07 田东 一种锂离子电池改性石墨负极材料的制备方法
CN109638268A (zh) * 2018-12-26 2019-04-16 赵宏伟 一种磷酸铋/磷酸铈复合锂电池正极材料及制备方法
CN113136106A (zh) * 2021-05-18 2021-07-20 湖南飞鸿达新材料有限公司 一种薄片型导热吸波复合材料
CN114538928A (zh) * 2022-04-25 2022-05-27 长沙中瓷新材料科技有限公司 石墨碳基匣钵

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09201525A (ja) * 1996-01-26 1997-08-05 Sumitomo Electric Ind Ltd ダイヤモンド焼結体の製造方法
JP2004299944A (ja) * 2003-03-31 2004-10-28 Jfe Chemical Corp 黒鉛質粒子、その製造方法、リチウムイオン二次電池およびその負極材料
WO2008084675A1 (ja) * 2006-12-26 2008-07-17 Mitsubishi Chemical Corporation 非水系二次電池用複合黒鉛粒子、それを含有する負極材料、負極及び非水系二次電池
CN104310979A (zh) * 2014-10-22 2015-01-28 华文蔚 一种功能陶瓷粉体材料及其制备方法和应用
WO2017206299A1 (zh) * 2016-06-03 2017-12-07 田东 一种锂离子电池改性石墨负极材料的制备方法
CN107056299A (zh) * 2017-04-21 2017-08-18 华东理工大学 一种新型生产高强度炭石墨材料的复合添加剂及该炭石墨材料的制备方法
CN109638268A (zh) * 2018-12-26 2019-04-16 赵宏伟 一种磷酸铋/磷酸铈复合锂电池正极材料及制备方法
CN113136106A (zh) * 2021-05-18 2021-07-20 湖南飞鸿达新材料有限公司 一种薄片型导热吸波复合材料
CN114538928A (zh) * 2022-04-25 2022-05-27 长沙中瓷新材料科技有限公司 石墨碳基匣钵

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
磷酸铈基纳米材料的制备及电化学传感性能研究;朱凯;中国优秀硕士学位论文全文数据库;B014-2652 *

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