CN115558470A - 一种硝酸盐改性钙基热化学储能材料及其制备方法 - Google Patents
一种硝酸盐改性钙基热化学储能材料及其制备方法 Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 51
- 239000011232 storage material Substances 0.000 title claims abstract description 36
- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 23
- -1 Nitrate modified calcium Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 22
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 22
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 9
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
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- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 claims abstract description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 8
- FUECGUJHEQQIFK-UHFFFAOYSA-N [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[W+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] FUECGUJHEQQIFK-UHFFFAOYSA-N 0.000 claims abstract description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims abstract description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 4
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZVUZTTDXWACDHD-UHFFFAOYSA-N gold(3+);trinitrate Chemical compound [Au+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O ZVUZTTDXWACDHD-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 4
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 claims abstract description 4
- KUJRRRAEVBRSIW-UHFFFAOYSA-N niobium(5+) pentanitrate Chemical compound [Nb+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUJRRRAEVBRSIW-UHFFFAOYSA-N 0.000 claims abstract description 4
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 claims abstract description 4
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims abstract description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 4
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 4
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 11
- 150000001669 calcium Chemical class 0.000 claims description 10
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- 239000002994 raw material Substances 0.000 claims description 3
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- 230000008020 evaporation Effects 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 238000005338 heat storage Methods 0.000 abstract description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
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- 230000004888 barrier function Effects 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种硝酸盐改性钙基热化学储能材料及其制备方法，属于热化学储能技术领域。该材料由氢氧化钙和金属硝酸盐经湿法混合而得。所述金属硝酸盐选自硝酸铁、硝酸钨、硝酸钛、硝酸铊、硝酸铌、硝酸锌、硝酸锂、硝酸铜、硝酸钪、硝酸铂、硝酸金、硝酸铈、硝酸镥、硝酸钇、硝酸钆、硝酸镉、硝酸钠、硝酸镧、硝酸银、硝酸锶、硝酸钡、硝酸铷中的一种或几种。所述金属硝酸盐占硝酸盐改性钙基热化学储能材料总质量的5%~20%。本发明储热所需温度可降低超过40℃，长时间远距离储热损失小，储热反应时间短；材料制备工艺简单、无需高温高压、生产便捷、安全可靠、能够实现规模化生产，环境污染小。
Description
技术领域
本发明属于热化学储能技术领域，具体涉及一种硝酸盐改性钙基热化学储能材料及其制备方法。
背景技术
热化学储能具有独特的优势，如储能密度高，在长时间远距离的储热过程中热损失小等，成为当前储能领域的研究热点之一。在热化学储能领域，以氢氧化钙/氧化钙/水为体系的储能系统是典型的中高温储能体系，该体系储能温度范围宽，储能温度在300多度到700度不等，放热温度从室温到700度，且具有较高的储能密度。但是该体系依然存在一些问题，如材料热导率低，易于团聚和烧结。
常见的氢氧化钙/氧化钙体系储能材料可通过商业购买和水热合成法获得，通过掺杂高热导率的功能材料，如金属氧化物/氢氧化物(MgO、LiOH等)、高导热率碳基材料(膨胀石墨、碳纳米管等)，可有效改善材料的热导率，一定程度上改善材料的循环稳定性。提高储能材料的比表面积/孔隙率来提高材料的性能。此外，功能材料的掺杂可有效降低钙基材料的反应起始温度，如武钦佩等通过对掺杂硝酸氧锆将氢氧化钙的脱水温度降低了61℃(Chemical Engineering Journal,2020,399,125841)，闫君等通过掺杂氢氧化锂有效地缩短了氢氧化钙的脱水反应时间(Chemical Engineering Science,2015,138,86-92)。高温水热合成法制备和功能材料掺杂得到的氢氧化钙都具有一定的抗团聚和耐烧结性，材料的使用寿命较长。
金属氧化物和氢氧化物掺杂可有效改善钙基材料的储能特性，但关于硝酸盐改善储能材料特性的研究较少。
发明内容
解决的技术问题：针对上述技术问题，本发明提供了一种硝酸盐改性钙基热化学储能材料及其制备方法，储热所需温度可降低超过40℃，长时间远距离储热损失小，储热反应时间短；材料制备工艺简单、无需高温高压、生产便捷、安全可靠、能够实现规模化生产，环境污染小。
技术方案：一种硝酸盐改性钙基热化学储能材料，由氢氧化钙和金属硝酸盐经湿法混合而得。
优选的，所述金属硝酸盐选自硝酸铁、硝酸钨、硝酸钛、硝酸铊、硝酸铌、硝酸锌、硝酸锂、硝酸铜、硝酸钪、硝酸铂、硝酸金、硝酸铈、硝酸镥、硝酸钇、硝酸钆、硝酸镉、硝酸钠、硝酸镧、硝酸银、硝酸锶、硝酸钡、硝酸铷中的一种或几种。
优选的，所述金属硝酸盐占硝酸盐改性钙基热化学储能材料总质量的5％～20％。
一种硝酸盐改性钙基热化学储能材料的制备方法，包括步骤如下：
S1.原料预处理：干燥氢氧化钙并研磨金属硝酸盐；
S2.湿法混合：将预处理后的氢氧化钙和金属硝酸盐溶解后超声搅拌，再经过蒸发、干燥和研磨获得所述硝酸盐改性钙基热化学储能材料。
优选的，所述步骤S1中，干燥条件为80～120℃下真空干燥2～6h。
优选的，所述步骤S2中，蒸发条件为80～95℃。
优选的，所述步骤S2中，干燥条件为120℃下真空干燥6～12h。
有益效果：利用本发明所提供的硝酸盐改性氢氧化钙储能材料，能够在较低的温度下实现蓄热应用，较低的蓄热温度对缓解钙基材料的团聚和烧结问题意义重大。
本发明使用的氢氧化钙为普通商业氢氧化钙，所有金属硝酸盐类为常见的盐类，采用的制备方法为简单的湿法混合法，制备工艺简单。金属硝酸盐改性对储能材料的反应焓影响较小，并不会牺牲储能材料的储能密度，但会大大降低储能材料的脱水反应温度。当掺杂摩尔比较低时，即可减低储能材料的储热反应起始温度，当掺杂比例进一步提高，起始温度下降更为明显。这对改善材料烧结问题，延长材料的使用寿命，提高材料的循环稳定性具有重要作用。
附图说明
图1是不同比例的硝酸钇掺杂下，样品的脱水反应DSC曲线图；
图2是不同硝酸盐掺杂下，样品的等温脱水反应动力学曲线图；
图3是不同元素掺杂下钙基储能材料的过渡态能垒。
具体实施方式
下面结合附图和具体实施例对本发明作进一步描述。
实施例1硝酸盐改性钙基热化学储能材料的制备
一种硝酸盐改性钙基热化学储能材料的制备方法，包括步骤如下：
S1.原料预处理：
干燥氢氧化钙：购买的氢氧化钙为分析纯度，质量百分比>95％，使用前不进一步提纯处理，只对其进行干燥处理，干燥条件是120℃下真空干燥2h；
研磨金属硝酸盐：由于部分硝酸盐中带有结晶水，容易形成大块结晶，因此用研钵研磨成细粉末，该处理的目的是让硝酸盐更易于溶解和称量；
S2.湿法混合：
取预处理后的氢氧化钙0.2g和金属硝酸盐(0～0.05g)混合，其中硝酸盐质量掺杂比为0～20wt％，在(10mL乙醇/5mL水)的乙醇水溶液中溶解，在烧瓶中超声搅拌30min，移入旋转蒸发器中，80～95℃下旋转蒸发除去溶剂，将浓缩的氢氧化钙/金属硝酸盐混合物移入干燥箱中，120℃下真空干燥6～12h，得到的样品经过研磨即获得所述硝酸盐改性钙基热化学储能材料。
表1硝酸盐掺杂比例
所述金属硝酸盐选自硝酸铁、硝酸钨、硝酸钛、硝酸铊、硝酸铌、硝酸锌、硝酸锂、硝酸铜、硝酸钪、硝酸铂、硝酸金、硝酸铈、硝酸镥、硝酸钇、硝酸钆、硝酸镉、硝酸钠、硝酸镧、硝酸银、硝酸锶、硝酸钡、硝酸铷中的一种或几种。
实施例2非等温脱水反应特性分析
以硝酸钇为掺杂硝酸盐为例，当硝酸盐的质量掺杂比例为5wt％～20wt％时，氢氧化钙的质量占比为80wt％～95wt％。脱水反应温度升高至120℃下保持20～30min，以除去物理吸附的水，升温速率为10℃/min，继续升温至550℃，得到储能材料的储热反应曲线。对比不同硝酸盐掺杂比例的脱水反应起始温度，如图1和表2所示。
表2不同硝酸钇质量掺杂比例下样品的起始反应温度Tonset
当掺杂比例为5wt％时，Tonset由纯氢氧化钙的376℃下降到363℃，当硝酸钇掺杂比例上升至15wt％～20wt％时，Tonset下降至331～332℃。建议掺杂比例为10wt％～15wt％，在此范围内储能材料的脱水反应起始温度可降低7％～12％，材料可适用温度范围扩大量和有效储能材料占比综合较好。
DSC测试结果表明，掺杂15wt％硝酸钇后，材料的反应焓与未掺杂样品相比，未掺杂氢氧化钙的脱水反应反应热为1079J/g，掺杂后样品的脱水反应热为1036J/g，变化较小。硝酸盐掺杂对氢氧化钙的储热密度影响较小，可以大幅度提高反应速率。
实施例3等温反应特性分析
在相同的较低的温度下，硝酸盐掺杂氢氧化钙具有更快的反应速率和转化率。当硝酸盐(Sc和Y)的掺杂比例为15wt％时，在320摄氏度下的脱水反应曲线(如图2所示)表明，在较低的温度下，掺杂硝酸盐后，储能材料的脱水速率大大提高。
实施例4第一性原理研究金属元素掺杂对热化学储能材料储能性能的影响
不同元素掺杂下，采用第一性原理计算得到储能材料反应能垒，如图3所示，图中可以看到，掺杂金属元素后，材料的脱水反应能垒显著降低。在DFT计算结果的指导下，较低的反应能垒意味着较低的反应起始温度，实验结果与计算结果相吻合。
Claims (7)
1.一种硝酸盐改性钙基热化学储能材料，其特征在于，由氢氧化钙和金属硝酸盐经湿法混合而得。
2.根据权利要求1所述的一种硝酸盐改性钙基热化学储能材料，其特征在于，所述金属硝酸盐选自硝酸铁、硝酸钨、硝酸钛、硝酸铊、硝酸铌、硝酸锌、硝酸锂、硝酸铜、硝酸钪、硝酸铂、硝酸金、硝酸铈、硝酸镥、硝酸钇、硝酸钆、硝酸镉、硝酸钠、硝酸镧、硝酸银、硝酸锶、硝酸钡、硝酸铷中的一种或几种。
3.根据权利要求1所述的一种硝酸盐改性钙基热化学储能材料，其特征在于，所述金属硝酸盐占硝酸盐改性钙基热化学储能材料总质量的5%~20%。
4.权利要求1所述的一种硝酸盐改性钙基热化学储能材料的制备方法，其特征在于，包括步骤如下：
S1.原料预处理：干燥氢氧化钙并研磨金属硝酸盐；
S2.湿法混合：将预处理后的氢氧化钙和金属硝酸盐溶解后超声搅拌，再经过蒸发、干燥和研磨获得所述硝酸盐改性钙基热化学储能材料。
5.根据权利要求4所述的一种硝酸盐改性钙基热化学储能材料的制备方法，其特征在于，所述步骤S1中，干燥条件为80 ~120℃下真空干燥2~6 h。
6.根据权利要求4所述的一种硝酸盐改性钙基热化学储能材料的制备方法，其特征在于，所述步骤S2中，蒸发条件为80~95℃。
7.根据权利要求4所述的一种硝酸盐改性钙基热化学储能材料的制备方法，其特征在于，所述步骤S2中，干燥条件为120 ℃下真空干燥6~12h。
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| US4338098A (en) * | 1979-04-03 | 1982-07-06 | Teitin Limited | Solid heat-generating composition |
| CN102060324A (zh) * | 2010-11-11 | 2011-05-18 | 刘秦 | 掺杂钛酸钡粉体的湿法制备方法 |
| CN109777373A (zh) * | 2019-03-06 | 2019-05-21 | 北京理工大学 | 中温跨季储热材料 |
| CN110257016A (zh) * | 2019-05-20 | 2019-09-20 | 北京理工大学 | 氢氧化物储热材料 |
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| US4338098A (en) * | 1979-04-03 | 1982-07-06 | Teitin Limited | Solid heat-generating composition |
| CN102060324A (zh) * | 2010-11-11 | 2011-05-18 | 刘秦 | 掺杂钛酸钡粉体的湿法制备方法 |
| CN109777373A (zh) * | 2019-03-06 | 2019-05-21 | 北京理工大学 | 中温跨季储热材料 |
| CN110257016A (zh) * | 2019-05-20 | 2019-09-20 | 北京理工大学 | 氢氧化物储热材料 |
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