CN110649304A - 锡-碘酸可充电电池 - Google Patents
锡-碘酸可充电电池 Download PDFInfo
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- DUAXTJAAJYSKAM-UHFFFAOYSA-N [Sn].I(=O)(=O)O Chemical compound [Sn].I(=O)(=O)O DUAXTJAAJYSKAM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 15
- 229910052718 tin Inorganic materials 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 4
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- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 3
- 229920000298 Cellophane Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229940005633 iodate ion Drugs 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001728 nano-filtration Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 10
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011630 iodine Substances 0.000 abstract description 7
- 229910052740 iodine Inorganic materials 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- -1 hydrogen ions Chemical class 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 2
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- 241001391944 Commicarpus scandens Species 0.000 description 1
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- 229920000557 Nafion® Polymers 0.000 description 1
- PMJHPLYNASCEAT-UHFFFAOYSA-N [Sn].[I] Chemical compound [Sn].[I] PMJHPLYNASCEAT-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 229960002358 iodine Drugs 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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Abstract
本发明公开一种可充电的锡‑碘酸电池，通过锡在负极氧化成亚锡离子而碘酸根在正极还原成碘和碘化物来产生电能。锡‑碘酸电池包括一个锡负极，一个碳正极，一个选择性透过隔膜和酸性水溶性电解液。这种电池主要用于大规模储能和电动汽车。
Description
技术领域
本发明属于电池技术领域，具体涉及以锡和碘酸盐为活性材料的可充电电池。
背景技术
人类社会的经济发展中，能源消耗越来越大。以化石燃料石油和煤为主的能源产生二氧化碳和烟雾，造成地球气候变暖和环境污染。人们急需开发利用可再生的清洁能源，如太阳能和风能，来代替石油和煤炭。然而，太阳能和风能等可再生能源有一个很大的缺点，就是不稳定、不连续、不可控。太阳光阴天和晚上就没有了，风也是时有时无。这样能源发电并大规模并入电网会给电网的安全和稳定运行带来严重冲击，因此需要大规模储能技术，把风力和太阳能发电高峰时产生的电能先储存起来，到用电高峰时再根据需要供电。现在有很多种储存电能的方法，包括抽水、压缩空气、飞轮、和蓄电池等等，但从能量效率、资金投入、使用周期、以及地点限制来说，蓄电池储存电能是最好的选择。
现在最广泛使用的蓄电池是用在汽车上的铅酸电池，这也是最古老的蓄电池。但是铅酸电池能量密度低，只有30-40Wh/kg，而且铅有毒，对环境有害。其它还有镍镉电池、镍氢电池、锂离子电池等等。这些电池具有更高的能量密度。然而，这些电池也有缺点。锂离子电池使用的有机电解液具有很高的毒性并且易燃，生产条件要求高，价格昂贵，一旦使用不当，如过放电、过充电、或短路，会造成电池损坏和严重的安全问题。其它镍镉、镍氢电池也存在有毒(镉)或电极存量小(金属氢)，以及充放电的记忆效应等的问题。这些电池不但使用稀有金属，如锂、钴、镉、镁、汞等，而且这些电极材料难以再利用回收，生产耗能高。
现在新能源汽车上主要也是使用锂电池，主要是因为其能量密度高的优点。但是电动汽车一旦发生碰撞事故，锂电池极易破碎引起大火燃烧。安全始终是一大隐患。而且锂电池冬天的时候气温低，性能大打折扣。
所以，现在新能源的发展急需一种安全、环保、能量密度高、功率密度高、而且还便宜的可充电蓄电池，用在大规模储能和新能源汽车上。目前还没有这样一种电池能很好地满足需要。本发明的目的就是提供这样一种电池。目前尚不存在本发明所公开的锡-碘酸电池。
发明内容
本发明的目的是提供一种安全环保、能量密度和功率密度高、并且成本低的可充电电池，用于大规模储能技术和新能源汽车。
这个目的的实现是通过本发明的锡-碘酸可充电电池，其包括一个锡负极、一个碳正极、一个选择性透过隔膜、以及酸性水溶性电解液。
所述锡负极含有锡金属、锡合金、碳毡、石墨毡、碳布、碳纸、碳钎维、多孔碳、或者锡粉和电子导电剂及粘结剂的压缩混合物。
所述碳正极含有碳钎维、碳毡、碳泡沫、石墨毡、碳布、碳纸、多孔碳、或者碳粉和电子导电剂及粘结剂的压缩混合物。
所述选择性透过隔膜可以是离子交换膜、反渗透膜(RO)、纳米过滤膜(NF)、半渗透膜、或玻璃纸，允许氢离子透过但阻挡其它离子通过。
所述酸性水溶性电解液包括负极锡电解液和正极碘酸电解液。
所述负极锡电解液至少包含一种硫酸、盐酸、硝酸、氨基磺酸、磷酸、乙酸、柠檬酸、亚锡盐。
所述正极碘酸电解液至少包括一种碘酸盐、碘化物、碘酸、碘。
所述锡-碘酸电池可以是普通电池，也可以是液流电池。液流电池更适合大规模电能储存和电动汽车。
附图说明
为了更好地理解本发明并且展示如何付诸实施，现在通过举例的方式参照附图描述本发明的具体实施方案。
图1.锡-碘酸液流电池
具体实施方式
以下通过实施例对本发明做进一步说明。
图1所示为锡-碘酸可充电液流电池。液流电池技术是一种新型的大规模高效储能技术。液流电池将电极和储能活性物质在空间上分离。活性物质储存于电解液储存罐中，循环流动。这样可以使电池功率与电池能量设计相对独立。功率由电极大小决定，而电池能量由储存罐大小决定，可以灵活地独立调整，适合大规模蓄电储能的要求。
如图1所示，在这个实施例中，负极1是锡，正极2是碳钎维，负极电解液是硫酸溶液，正极电解液是碘酸钾溶液。选择性透过隔膜3是质子交换膜Nafion N115。锡-碘酸电池构成以下氧化还原反应：
负极：
E0＝-0.13V
正极：
E0＝1.20V
总反应：
E＝1.33/0.67V
在放电过程中，负极电解液中的氢离子穿过隔膜进入正极电解液参与电化学反应。负离子碘酸根离子、碘离子和碘都不能透过隔膜。在充电过程中，氢离子回到负极电解液而碘离子和碘在催化剂的作用下被氧化成碘酸根离子。电池开路电压1.55伏，高于标准电位的1.33 伏。
电池电化学反应也可以从亚锡离子电解液以及碘/碘化物电解液充电开始，反应原理和过程都是一样的。选择性透过隔膜可以是一层膜，也可以是多层膜合在一起。
锡的标准电极电势很低，一般电池很少考虑选用锡做负极材料。然而，碘酸根有很高的能量密度和水溶解度，但是需要非常酸性的环境。只有锡能够承受这么酸性的环境。为了利用碘酸根，不得不利用锡做负极。好消息是实际开路电压1.55伏高于预期，并且亚锡盐的高溶解度导致了高的电池能量密度。
电池能量密度一般用单位质量反应物质所储存的能量来描述，可以由活性物质的浓度和电池电压来计算：
其中N是电子数，这里是12，F是法拉第常数(26.8Ah mol-1)，V是电压，m是总质量包括溶剂水，取决于参与反应物质的溶解度。
因此锡-碘酸电池的理论能量密度可以计算出来为170Wh/kg。实际能量密度可以达到 90Wh/kg。这个能量密度远高于现有的铅酸电池(30Wh/kg)和全钒液流电池(25-30Wh/kg)，接近锂离子电池(100-265Wh/kg)。
实验表明锡-碘酸电池可以200mA/cm2的速度快速充放电，因此具有高的功率密度。锡和碘都是无毒的，可循环利用的，而且水溶性也不会燃烧，这些都使这种电池很安全而且对环境无害。并且锡和碘都不是非常昂贵，制造成本低。这些特性使锡-碘电池几乎完美地适合大规模储能和新能源汽车。
尽管在这个实施例的基础上，对本发明进行了详细的讲解，应该明白的是这些细节只是为了说明的目的，本发明并不限于这个实施例。相反地，本发明涵盖在权利要求书范围内的所有改进和类似安排。
Claims (7)
1.一种可充电锡-碘酸电池，包括普通电池和液流电池，用于以高能量密度和功率密度储存电能，包含：
一个锡负极，
一个碳正极，
一个选择性透过隔膜，
酸性水溶性电解液。
2.根据权利要求1所述的锡-碘酸电池，其特征在于所述锡负极至少包含以下一种材料：锡、锡合金、石墨毡、碳毡、碳布、碳纸、碳钎维、多孔碳、或锡粉和电子导电剂及粘结剂的压缩混合物。
3.根据权利要求1所述的锡-碘酸电池，其特征在于所述碳正极至少包含以下一种材料：碳钎维、碳毡、石墨毡、碳泡沫、碳布、碳纸、多孔碳、或碳粉和电子导电剂及粘结剂的压缩混合物。
4.根据权利要求1所述的锡-碘酸电池，其特征在于所述选择性透过隔膜至少包含以下一种膜：离子交换膜、反渗透膜、纳米过滤膜、半渗透膜、玻璃纸。
5.根据权利要求1所述的锡-碘酸电池，其特征在于所述酸性水溶性电解液包括负极亚锡离子电解液和正极碘酸根离子电解液。
6.根据权利要求5所述的锡-碘酸电池，其特征在于所述负极亚锡离子电解液至少包含以下一种物质：硫酸、盐酸、硝酸、氨基磺酸、磷酸、乙酸、柠檬酸、亚锡盐。
7.根据权利要求5所述的锡-碘酸电池，其特征在于所述正极碘酸根电解液至少包含以下一种物质：碘酸盐、碘化物、碘、碘酸。
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