CN111653790A - 一种全固态铁空电池 - Google Patents
一种全固态铁空电池 Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 10
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- -1 oxygen ions Chemical class 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 6
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 6
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 5
- 239000002001 electrolyte material Substances 0.000 claims abstract description 3
- 238000009413 insulation Methods 0.000 claims abstract description 3
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 claims description 42
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 37
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 13
- 239000004332 silver Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000010416 ion conductor Substances 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 241000968352 Scandia <hydrozoan> Species 0.000 claims description 2
- CJDIITMOUDHXLO-UHFFFAOYSA-N [Co]=O.[Fe].[Sr].[Ba] Chemical compound [Co]=O.[Fe].[Sr].[Ba] CJDIITMOUDHXLO-UHFFFAOYSA-N 0.000 claims description 2
- YVCLIGOJWULNFL-UHFFFAOYSA-N [Co]=O.[Fe].[Sr].[La] Chemical compound [Co]=O.[Fe].[Sr].[La] YVCLIGOJWULNFL-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- PIRUAZLFEUQMTG-UHFFFAOYSA-N lanthanum;oxomanganese;strontium Chemical compound [Sr].[La].[Mn]=O PIRUAZLFEUQMTG-UHFFFAOYSA-N 0.000 claims description 2
- HJGMWXTVGKLUAQ-UHFFFAOYSA-N oxygen(2-);scandium(3+) Chemical compound [O-2].[O-2].[O-2].[Sc+3].[Sc+3] HJGMWXTVGKLUAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910002076 stabilized zirconia Inorganic materials 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052742 iron Inorganic materials 0.000 abstract description 10
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 238000011160 research Methods 0.000 description 7
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- 241000233855 Orchidaceae Species 0.000 description 5
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- 150000002500 ions Chemical class 0.000 description 4
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- 230000033116 oxidation-reduction process Effects 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
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- 229910052684 Cerium Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 239000002918 waste heat Substances 0.000 description 1
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Abstract
本发明涉及一种全固态铁空电池，其包括正极、负极、隔膜和固态电解质，其中，正极和负极分别设置于固态电解质的相对两侧，隔膜被设置于负极和固态电解质之间形成夹层结构，负极为碱金属掺杂的氧化铁形成的铁酸盐材料，正极为具有高效氧化还原催化活性的金属或金属氧化物材料，固态电解质为能够高效传导氧离子的电解质材料，隔膜为薄膜状或片状的具有氧离子传导性和电子绝缘性的材料。根据本发明的全固态铁空电池，负极通过碱金属掺杂进入氧化铁晶格中，能够显著提高铁电极的电化学反应活性，改善电池过充带来的安全隐患问题，进而显著提高铁空电池的性能，隔膜设置于固体电解质与负极之间，能够有效缓解电池漏电问题。
Description
技术领域
本发明涉及铁空电池，更具体地涉及一种全固态铁空电池。
背景技术
金属空气电池是一种利用金属的氧化还原过程实现电池充放电的储能技术，其容量远远高于常规的电池储能技术，特别适合于大规模电网储能领域。铁是地壳中含量第四的元素，它储量丰富、有多种稳定的氧化态、成本低，易氧化，是一种很有潜力的金属电极材料。铁空电池的理论能量密度为2000Wh/kg，这个数值足够适应一系列储能应用。
高温的条件能够明显提高电化学反应速率，尽可能地利用活性物质氧化还原反应产生的能量，有效提高电池的能量利用率。近些年，基于工业废热、余热等能源综合利用政策，有关高温电池的研究也在加大投入，关于高温铁空电池的研究工作也有相关报道。2013年起，美国乔治华盛顿大学Stuart Licht的团队以熔融的Li2CO3盐、Li0.87Na0.63K0.5CO3共晶熔盐作为电解质设计组装了高温熔盐铁空电池，实现了熔盐电池的大电流循环充放电。2017年，中国科学院上海应用物理研究所的研究团队设计以高温导电陶瓷YSZ片隔绝液态熔盐与电池正极，提出了双相电解质的高温熔盐铁空电池概念。然而，液态熔盐极易流动，只能用于静态储能，液态熔盐难以支撑正负极，使得高温铁空电池的放大存在技术性的难题，另外，由于铁空电池的正极活性物质为空气，使得其正极部分是裸露在空气中的，形成了半开放的电池结构，然而高温下液态熔盐极易挥发，半开放的电池结构存在电解液干涸的安全隐患，因此对于电池的密封也是必不可少的，而高温熔盐对于正极材料以及密封材料的腐蚀问题也是影响电池长期运行稳定性的重要因素。针对以上存在的问题，不难发现，将高温熔盐电池用于大型储能领域相对于常规的电池具有更大的难度。考虑以固态电解质替换液态熔盐能够有效解决高温熔盐带来的一系列问题。有关高温全固态铁空电池研究主要以近两年意大利CNR-ITAE的工作较为突出，他们设计以600-800℃范围内具有优异的氧离子传导性能的La0.8Sr0.2Ga0.8Mg0.2O3(LSGM)作为电解质，混合了Fe2O3的C0.8Gd0.2O2(Fe-CGO)作为负极，La0.6Sr0.4Fe0.8Co0.2O3(LSFCO)作为空气电极的全固态铁空电池，电池的实际能量密度高达460Wh/kg，容量高达0.5Ah/g，对比其他类型的电池性能有了极大的提升。
然而，相比于铁空电池的理论参数，全固态铁空电池的提升空间依旧很大。负极活性物质氧化铁与CGO粉体简单混合，在电池工作过程中，铁的氧化还原反应极易导致氧化铁与CGO的分层，从而极大地增加电池内阻，增大电池内部消耗，影响电池性能。因此，制备高效铁氧化还原催化活性的负极材料至关重要。另外，铁空电池的理论开路电压为1.2V，而固态电解质中的Ce离子在高于1V的电压下极易被还原为金属铈，增大了电解质的电子传导性，使得电池工作过程中存在漏电行为，降低了电池寿命。
发明内容
为了解决现有技术中的负极活性低和电池漏电等问题，本发明提供一种全固态铁空电池。
根据本发明的全固态铁空电池，其包括正极、负极、隔膜和固态电解质，其中，正极和负极分别设置于固态电解质的相对两侧，隔膜被设置于负极和固态电解质之间形成夹层结构，负极为碱金属掺杂的氧化铁形成的铁酸盐材料，正极为具有高效氧化还原催化活性的金属或金属氧化物材料，固态电解质为能够高效传导氧离子的电解质材料，隔膜为薄膜状或片状的具有氧离子传导性和电子绝缘性的材料。
本发明借鉴高温固体氧化物燃料电池(SOFC)技术，在高温铁空电池中引入了能够高效传导氧离子的全固态电解质，同时利用碱金属掺杂的氧化铁材料作为负极，提供一种全新的稳定的全固态铁空电池结构。特别地，SOFC的正负极活性物质都是气体，而本发明的高温铁空电池其负极端活性物质为铁，其状态一般为固态，这就涉及到在SOFC的研究中并不需要涉及的有关铁电极的活性问题。而且，本发明创新性地引入隔膜以改善过充电带来的电解质漏电行为。
优选地，正极选自由银(Ag)、铂(Pt)、镧锶锰氧(LSM)、镧锶铁钴氧(LSFCO)和钡锶钴铁氧(BSCF)组成的组中的至少一种金属以及金属氧化物导电材料。应该理解，正极还可以是其他具有高效氧催化活性的金属以及金属氧化物材料。
优选地，固态电解质为适用于600-1000℃温度区间内的氧离子导体。相对应地，全固态铁空电池的工作温度区间为600-1000℃。
优选地，固态电解质选自由掺杂的氧化铈(GDC、SDC)、碱金属掺杂的镧镓氧(LSGM)、氧化钇稳定的氧化锆(YSZ)和氧化钪稳定的氧化锆(SSZ)组成的组中的至少一种氧离子导体。
优选地，固态电解质中混有2-4wt％的氧化钇稳定的氧化锆(YSZ)或二氧化锆(ZrO2)。这对于提高全固态铁空电池的过充电的耐受性是特别有利的。在一个优选的实施例中，固态电解质为GDC和YSZ的混合物，其中，YSZ含量为3wt％。
优选地，隔膜为二氧化锆(ZrO2)或氧化钇稳定的氧化锆(YSZ)。更优选地，隔膜为致密的片状或薄膜材料，可利用涂覆、蒸镀、沉积等方式得到不同的厚度。特别地，考虑到固态电解质，如GDC、SDC、LSGM在高于1.05V的电压时极易发生Ce的还原，使得电解质的电子传导率增强，隔膜能够有效隔绝正负极，减弱内部电子传导性，降低电池内部电荷损失。
优选地，负极选自由钾掺杂的氧化铁、钠掺杂的氧化铁和锂掺杂的氧化铁组成的组中的至少一种铁酸盐材料。特别地，氧化铁本身导电性以及催化活性很低，经碱金属掺杂的氧化铁材料在导电性以及催化活性方面均有较大的提升。更优选地，通过熔盐法在氧化铁中掺杂碱金属。
优选地，负极中混有氧化钇稳定的氧化锆(YSZ)或二氧化锆(ZrO2)。这对于改善负极与隔膜的接触是特别有利的。更优选地，负极为钾掺杂的氧化铁和氧化钇稳定的氧化锆(YSZ)的混合物、钠掺杂的氧化铁和二氧化锆(ZrO2)的混合物、锂掺杂的氧化铁和氧化钇稳定的氧化锆(YSZ)的混合物。更优选地，钾掺杂的氧化铁与YSZ的摩尔比为1:1，钠掺杂的氧化铁与ZrO2的摩尔比为1:1，锂掺杂的氧化铁与YSZ的摩尔比为2:1。应该理解，YSZ的混入还可以提高负极的导电性。
优选地，全固态铁空电池还包括相对两端直接连接负极和正极的引线。
优选地，引线为Ag丝、不锈钢、或Ni线。
根据本发明的全固态铁空电池，负极通过碱金属掺杂进入氧化铁晶格中，可明显增加氧化铁晶胞体积，在铁的嵌入/脱除过程中能够保持晶胞完整性，使得在电池充放电过程中不至于由于铁的氧化还原而发生晶格坍塌的问题，有效提高电池结构稳定性，即能够显著提高铁电极的电化学反应活性，改善电池过充带来的安全隐患问题，进而显著提高铁空电池的性能。根据本发明的全固态铁空电池，隔膜在高温下优异的氧离子传导性能，同时其电势窗口大于铁的氧化还原电位，设置于固体电解质与负极之间能够有效缓解电池漏电问题。总之，根据本发明的全固态铁空电池，不使用液态电解质能够有效解决电池不易移动、电解液挥发干涸导致正负极接触从而发生短路的问题，具有良好的氧离子传导率，不存在高温熔盐易挥发、流动、腐蚀的问题，显著降低了电池成本，同时使用高效的负极材料以及添加隔膜降低电池漏电行为，安全性高、绿色环保、使用寿命长。
附图说明
图1是根据本发明的一个优选实施例的全固态铁空电池的结构示意图；
图2是根据本发明的实施例1的电池充放电曲线示意图；
图3是根据本发明的实施例2的电池充放电曲线示意图；
图4是根据本发明的实施例3的电池充放电曲线示意图；
图5是根据本发明的实施例4的电池充放电曲线示意图；
图6是根据本发明的实施例5的电池充放电曲线示意图。
具体实施方式
下面结合附图，给出本发明的较佳实施例，并予以详细描述。
如图1所示，根据本发明的一个优选实施例的全固态铁空电池包括负极1、隔膜2、固态电解质3、正极4和引线5，其中，负极1和正极4分别设置于固态电解质3的相对两侧，隔膜2被设置于负极1和固态电解质3之间形成夹层结构，引线5的相对两端直接连接负极1和正极4。
实施例1
负极1为钾掺杂的氧化铁+YSZ(1:1)，隔膜2为ZrO2，固态电解质3为GDC，正极4为Ag，引线5为Ag。
通过离子溅射的方法将ZrO2沉积在GDC片的表面，再将负极涂敷在ZrO2上，将银浆涂在GDC另一侧，最后用银线引出导线，银线的固定用银浆粘贴。待银浆固化后将电池放入600℃的电炉中恒温，进行充放电测试。测试时，使用中国兰电电池测试系统的工作电极分别与电池的正负极相联，设置充电电流为10mA，充电时间为30min，放电电流为10mA，放电终止电压为0.3V，得到电池的充放电曲线。
如图2的GDC电解质充放电曲线所示，充电电流为10mA，充电电压约为1.08V，放电电流为10mA，放电终止电压约为0.3V。
实施例2
负极1为钠掺杂的氧化铁+ZrO2(1:1)，隔膜2为ZrO2，固态电解质3为LSGM，正极4为Ag，引线5为Ag。
通过原子层沉积技术将ZrO2沉积在LSGM片的表面，再将负极涂敷在ZrO2上，将Ag浆涂在LSGM另一侧，最后用银线引出导线，银线的固定用银浆粘贴。待银浆固化后将电池放入750℃的电炉中恒温，进行充放电测试。测试时，使用中国兰电电池测试系统的工作电极分别与电池的正负极相联，设置充电电流为10mA，充电时间为30min，放电电流为10mA，放电终止电压为0.3V，得到电池的充放电曲线。
如图3的LSGM电解质充放电曲线所示，充电电流为10mA，充电电压约为1.13V，放电电流为10mA，放电终止电压约为0.3V。
实施例3
负极1为锂掺杂的氧化铁+YSZ(2:1)，隔膜2为ZrO2，固态电解质3为YSZ，正极4为Ag，引线5为Ag。
通过原子层沉积技术将ZrO2沉积在YSZ片的表面，再将负极涂敷在ZrO2上，将Ag浆涂在YSZ另一侧，最后用银线引出导线，银线的固定用银浆粘贴。待银浆固化后将电池放入850℃的电炉中恒温，进行充放电测试。测试时，使用中国兰电电池测试系统的工作电极分别与电池的正负极相联，设置充电电流为10mA，充电时间为30min，放电电流为10mA，放电终止电压为0.3V，得到电池的充放电曲线。
如图4的YSZ电解质充放电曲线所示，充电电流为10mA，充电电压约为1.15V，放电电流为10mA，放电终止电压约为0.3V。
实施例4
负极1为钾掺杂的氧化铁+YSZ(1:1)，隔膜2为ZrO2，固态电解质3为YSZ，正极4为Ag，引线5为Ag。
通过离子溅射法将ZrO2沉积在YSZ片的表面，再将负极涂敷在YSZ上，将Ag浆涂在YSZ另一侧，最后用银线引出导线，银线的固定用银浆粘贴。待银浆固化后将电池放入850℃的电炉中恒温，进行充放电测试。测试时，使用中国兰电电池测试系统的工作电极分别与电池的正负极相联，设置充电电流为10mA，充电时间为60min，放电电流为10mA，放电终止电压为0.5V，得到电池的充放电曲线。
如图5的氧化铁电极充放电曲线所示，充电电流为10mA，充电电压约为1.18V，放电电流为10mA，放电终止电压约为0.5V。
实施例5
负极1为钾掺杂的氧化铁+YSZ(1:1)，隔膜2为YSZ，固态电解质3为GDC+YSZ(YSZ含量为3wt％)，正极4为Ag，引线5为Ag。
通过离子溅射法将YSZ沉积在GDC+YSZ片的表面，再将负极涂敷在YSZ上，将Ag浆涂在GDC+YSZ另一侧，最后用银线引出导线，银线的固定用银浆粘贴。待银浆固化后将电池放入850℃的电炉中恒温，进行充放电测试。测试时，使用中国兰电电池测试系统的工作电极分别与电池的正负极相联，设置充电电流为10mA，充电时间为30min，放电电流为10mA，放电终止电压为0.3V，得到电池的充放电曲线。
如图6的YSZ隔膜充放电曲线所示，充电电流为10mA，充电电压约为1.15V，放电电流为10mA，放电终止电压约为0.5V。
以上所述的，仅为本发明的较佳实施例，并非用以限定本发明的范围，本发明的上述实施例还可以做出各种变化。即凡是依据本发明申请的权利要求书及说明书内容所作的简单、等效变化与修饰，皆落入本发明专利的权利要求保护范围。本发明未详尽描述的均为常规技术内容。
Claims (10)
1.一种全固态铁空电池，其特征在于，该全固态铁空电池包括正极、负极、隔膜和固态电解质，其中，正极和负极分别设置于固态电解质的相对两侧，隔膜被设置于负极和固态电解质之间形成夹层结构，负极为碱金属掺杂的氧化铁形成的铁酸盐材料，正极为具有高效氧化还原催化活性的金属或金属氧化物材料，固态电解质为能够高效传导氧离子的电解质材料，隔膜为薄膜状或片状的具有氧离子传导性和电子绝缘性的材料。
2.根据权利要求1所述的全固态铁空电池，其特征在于，正极选自由银、铂、镧锶锰氧、镧锶铁钴氧和钡锶钴铁氧组成的组中的至少一种金属以及金属氧化物导电材料。
3.根据权利要求1所述的全固态铁空电池，其特征在于，固态电解质为适用于600-1000℃温度区间内的氧离子导体。
4.根据权利要求1所述的全固态铁空电池，其特征在于，固态电解质选自由掺杂的氧化铈、碱金属掺杂的镧镓氧、氧化钇稳定的氧化锆和氧化钪稳定的氧化锆组成的组中的至少一种氧离子导体。
5.根据权利要求1所述的全固态铁空电池，其特征在于，固态电解质中混有2-4wt％的氧化钇稳定的氧化锆或二氧化锆。
6.根据权利要求1所述的全固态铁空电池，其特征在于，隔膜为二氧化锆或氧化钇稳定的氧化锆。
7.根据权利要求1所述的全固态铁空电池，其特征在于，负极选自由钾掺杂的氧化铁、钠掺杂的氧化铁和锂掺杂的氧化铁组成的组中的至少一种铁酸盐材料。
8.根据权利要求1所述的全固态铁空电池，其特征在于，负极中混有氧化钇稳定的氧化锆或二氧化锆。
9.根据权利要求1所述的全固态铁空电池，其特征在于，全固态铁空电池还包括相对两端直接连接负极和正极的引线。
10.根据权利要求1所述的全固态铁空电池，其特征在于，引线为Ag丝、不锈钢、或Ni线。
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