WO2010069209A1 - 低自放电铁电极材料 - Google Patents

低自放电铁电极材料 Download PDF

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WO2010069209A1
WO2010069209A1 PCT/CN2009/074716 CN2009074716W WO2010069209A1 WO 2010069209 A1 WO2010069209 A1 WO 2010069209A1 CN 2009074716 W CN2009074716 W CN 2009074716W WO 2010069209 A1 WO2010069209 A1 WO 2010069209A1
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iron
electrode material
compound
content
low self
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PCT/CN2009/074716
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French (fr)
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陶明大
何秀能
潘唯
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成都和能科技有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/248—Iron electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an iron electrode material, and more particularly to a low self-discharge iron electrode material for use in the manufacture of an environmentally friendly iron-nickel battery.
  • the iron-nickel battery was invented by Edison in 1900. Between 1910 and 1960, iron-nickel batteries were widely used as traction power sources for traction locomotives. However, after 1960, research on iron-nickel batteries has been reduced, mainly because cadmium-nickel batteries have better performance than iron-nickel. With the continuous advancement of society, people's requirements for environmental protection are getting higher and higher. The cadmium-nickel batteries and lead-acid batteries that were heavily contaminated with heavy metals will be replaced by environmentally-friendly batteries. The iron-nickel battery just meets this. Claim.
  • the iron-nickel battery is a green secondary battery, which is a negative electrode active material of iron or iron, nickel oxyhydroxide as a positive electrode active material, and a sodium hydroxide (potassium) aqueous solution as an electrolyte.
  • the iron-nickel battery is divided into two types: a bag type battery and a plate type battery.
  • the bag battery is characterized by a long life, but lower specific energy, while the plate battery is just the opposite, the life is lower than the bag type, but the specific energy is higher.
  • iron-nickel batteries have obvious advantages: (1) There is no pollution to the environment.
  • iron-nickel batteries do not contain toxic heavy metal elements such as mercury, lead and cadmium, and no toxic gases and water are produced during the production process.
  • toxic heavy metal elements such as mercury, lead and cadmium
  • the life of cadmium-nickel batteries is more than 500 times
  • the life of lead-acid batteries is more than 250 times
  • the life of bag-type iron-nickel batteries can reach 2000-4000 times
  • the usage time can reach 10-25 years.
  • the theory is higher than the energy.
  • the positive electrode of the iron-nickel battery is the same as the positive electrode of the cadmium-nickel battery and the nickel-hydrogen battery, but the theoretical capacity of the iron electrode is as high as 1280 mAh/g, which is 2.67 times the theoretical capacity of the cadmium electrode and 3.56 times the theoretical capacity of the hydrogen electrode. (4) The price is moderate. Of all the electrode materials, the price of iron is the cheapest. Compared with nickel-hydrogen batteries and lithium-ion batteries, iron-nickel batteries also have a very low price. Compared with lead-acid batteries, the price of iron-nickel batteries is slightly higher, but its long life can fully compensate for this higher price.
  • iron-nickel batteries there are still some problems in iron-nickel batteries, including: (1) The self-discharge of the battery is large, and the self-discharge rate of the electrode is about 50 after 28 days at 20 °C. % (2) Poor performance in high current discharge and low temperature discharge. (3) The battery is less efficient to charge. (4) The utilization rate of the active material of the iron electrode is low. Generally only 10-20%. This greatly limits the specific energy of the iron-nickel battery. These problems are caused by the iron electrode.
  • the object of the present invention is to solve the problem of large self-discharge of an iron electrode, and to provide a low self-discharge iron electrode material.
  • the charged iron electrode is placed at 20 ° C for 28 days, the electrode
  • the self-discharge rate is less than 20%, and has the advantages of low cost and no pollution of heavy metals.
  • the low self-discharging iron electrode material of the present invention is composed of an active material and an additive.
  • the active material is a compound of iron or iron, including Fe 3 0 4 , Fe(OH) 2 , Fe(OH) 3 , Fe 2 0 3 ,
  • One or more of reduced iron powder, carbonyl iron powder; additives include: 1) a compound having a content of 0.02-0.15% of indium or indium, including In, ln 2 0 3 , In 2 (S04) 3 , In ( OH) 3 , InCl 3
  • a compound having a content of 2-8% tin or tin including one or more of Sn, SnO, SnO 2 , SnCl 2 , SnCl 4 and stannate,
  • a method for preparing the active material Fe 3 0 4 is exemplified: (1) A ferrous sulfate solution having a density of 1.24 - 1.26 g/cm 3 is prepared using purified water and technical grade ferrous sulfate.
  • the iron electrode of the present invention has an advantage in self-discharge as compared with a conventional iron electrode.
  • Figure 1 Low self-discharge iron electrode and ordinary iron electrode material 0.2C (60mA/g) discharge curve at 20 °C.
  • Example: The chemical composition of the high capacity iron electrode material of the present invention is: [14] The content of Fe 3 0 4 prepared according to the above formula is 82-90%, the content of In 2 0 3 is 0.05-0.07%, and the content of SnO is 3-
  • the iron electrode was prepared: (1) Weigh a quantity of Fe 3 0 4, Fe 3 0 4 in amounts of 0.05-0.07% of added In203, 3-5% of SnO, 2-4% of Bi 2 0 3
  • the iron electrode obtained above is used as the working electrode, the sintered nickel hydroxide electrode is used as the auxiliary electrode, and the capacity of the auxiliary electrode far exceeds the capacity of the iron electrode, so the auxiliary electrode can be used.
  • the electrolytic solution was a 6 mol/L KOH solution containing 15 g/L of LiOH.H 2 0, and the separator was a polypropylene felt.
  • the electrochemical performance test equipment is a domestic DC-5 battery performance tester. The activation system was first activated 6 times with 0.2 C and the ambient temperature was 25 °C. 0.2C
  • the charging current is 100 mA ⁇ g - 1 , charging for 6 h, the discharge current is 6 ⁇ ⁇ ⁇ ⁇ ⁇ , and the discharge cut-off potential is 1.0 V.
  • the sixth discharge capacity is the initial capacity Q Q of the electrode.
  • the self-discharge test method is: After charging the electrode as described above, at 20
  • Self-discharge rate (Oo-Qi) / Q 0 .
  • the iron electrode material of the present invention is left at 20 ° C for 28 days.
  • the self-discharge rate is less than 20%, and the self-discharge rate of ordinary iron electrode materials is about 50%.

Description

1氐自放电铁电极材料
4氐自放电铁电极材料
[1] 技术领域
[2] 本发明涉及一种铁电极材料， 特别是涉及一种低自放电铁电极材料， 该电极材 料用于制造环保型铁镍电池。
[3] 背景技术
[4] 铁镍电池是爱迪生在 1900年发明的。 在 1910至 1960年之间， 铁镍电池广泛用于 牵引机车作为动力电源。 但 1960年以后， 人们对铁镍电池的研究有所减少， 主要原因是镉镍电池具有比铁镍更好的性能。 随着社会的不断进步， 人们对环 境保护的要求也越来越高， 原来釆用的有重金属污染的镉镍电池及铅酸电池将 被环保型的电池取代， 铁镍电池正好满足了这一要求。
[5] 铁镍电池属于绿色环保二次电池， 该电池是以铁或铁的化合物作为负极活性物 质， 氢氧化亚镍为正极活性物质， 氢氧化钠 （钾） 水溶液为电解质。 按照电极 的制备工艺不同， 铁镍电池分为袋式电池和板式电池两种类型。 袋式电池的特 点是寿命很长， 但比能量较低， 而板式电池正好相反， 寿命相对袋式来说要低 一些， 但比能量较高。 与传统的铅酸电池和镉镍电池相比， 铁镍电池具有明显 的优点： （1) 对环境没有污染。 铁镍电池所用的材料均不含汞、 铅和镉等有毒 的重金属元素， 生产过程中也无有毒的气体和水产生。 （2) 寿命很长。 镉镍电 池的寿命为大于 500次， 铅酸电池的寿命为大于 250次， 袋式铁镍电池的寿命可 达到 2000-4000次， 使用吋间可达 10-25年。 （3) 理论比能量高。 铁镍电池的正 极与镉镍电池和氢镍电池的正极相同， 但铁电极的理论容量高达 1280mAh/g， 是 镉电极理论容量的 2.67倍， 是氢电极理论容量的 3.56倍。 (4) 价格适中。 在所 有的电极材料中， 铁的价格是最便宜的。 与氢镍电池和锂离子电池相比， 铁镍 电池还具有价格很低的特点。 与铅酸电池相比， 铁镍电池的价格虽然稍高， 但 其超长的寿命完全可以弥补高出的这部分价格。 但铁镍电池也还存在一些问题 ， 包括： （1) 电池的自放电大， 在 20°C条件下 28天后电极的自放电率大约为 50 % (2) 大电流放电和低温放电性能较差。 （3) 电池的充电效率较低。 (4) 铁 电极的活性物质利用率低。 一般只有 10-20%。 这就极大地限制了铁镍电池比能 量的提高。 这些问题都是由于铁电极引起的。
[6] 发明内容
[7] 本发明目的在于解决铁电极自放电大的问题， 提供一种低自放电的铁电极材料
， 充电态铁电极在在 20°C下搁置 28天后， 电极的
自放电率低于 20%， 且具有成本很低和没有重金属的污染的优点。
[8] 本发明低自放电铁电极材料由活性物质及和添加剂组成。 活性物质的成分是铁 或铁的化合物， 包括 Fe304，Fe(OH)2，Fe(OH) 3，Fe203，
还原铁粉， 羰基铁粉中的一种或几种； 添加剂包括： 1) 含量为 0.02-0.15%的铟 或铟的化合物， 包括 In、 ln203、 In2(S04)3、 In(OH)3、 InCl3
等中的一种或几种， 2) 含量为 2-8%的锡或锡的化合物， 包括 Sn、 SnO、 Sn02、 SnCl2、 SnCl4及锡酸盐中的一种或几种，
3) 含量为 1-7%的铋或铋的化合物， 包括 Bi、 Bi203、 Bi(N03)3等中的一种或几种 ， 4) 含量为 5- 10%的石墨粉。 由于直接购买的铁化合物杂质含量较高， 活性很 差， 因此一般需要自行制备。 举例说明活性物质 Fe304的制备方法： （1) 用净化 水和工业级硫酸亚铁配制密度为 1.24- 1.26g/cm3的硫酸亚铁溶液。 （2) 用净化水 和工业级氢氧化钠配制密度为 1.13- 1.15g/cm3的氢氧化钠溶液。 （3) 将硫酸亚铁 溶液加热至 90-98°C， 将氢氧化钠以喷淋的方式加入到硫酸亚铁溶液中， 同吋在 溶液中鼓入空气。 （4) 待氢氧化钠加完后， 加入硫酸亚铁含量 1-5%的乙炔黑， 再鼓入空气半小吋。 （5) 用化纤帆布过滤所得的浆料， 并用净化水洗涤沉淀至 不含硫酸根。 （6) 将沉淀烘干后， 放到 780-880°C的条件下还原。 （7) 将还原 后的物质粉碎至过 20目筛， 得到所需要的铁电极活性物质。
[9] 与普通的铁电极相比， 本发明铁电极的优点是自放电低。
[10] 附图说明
[11] 图 1 : 低自放电铁电极与普通铁电极材料 20°C下 0.2C (60mA/g) 放电曲线。
[12] 具体实施方式
[13] 实施例： 本发明高容量铁电极材料的化学组成为： [14] 按上述方制得的 Fe304含量为 82-90% , In203的含量为 0.05-0.07%.， SnO含量为 3-
5% , Bi203的含量为 2-4% , 石墨粉的含量为 6-8%。
[15] 铁电极的制备方法是： （1) 称取一定量的 Fe304， 按 Fe304的量加入 0.05-0.07% 的 In203， 3-5%的 SnO， 2-4%的 Bi203
。 7-8%的石墨粉。 （2) 再加放一定量的浓度为 5-10%PVA粘结剂， 搅拌均匀后 ， 将浆料涂在负极集流体上 （集流体是泡沫镍、 泡沫铁或钢带中的一种） 。 （3 ) 将电极烘干后， 在液压机上用 24MPa的压力将电极压成型。
[16] 铁电极的充放电试验： 将上述制得到的铁电极作为工作电极， 烧结式氢氧化亚 镍电极为辅助电极， 且辅助电极的容量远远超过铁电极的容量， 因此可将辅助 电极作为参比电极， 电解液为 6mol/L KOH溶液 （其中含有 15g /L的 LiOH.H2 0) ， 隔膜为聚丙烯毡。 电化学性能测试设备为国产 DC-5型电池性能测试仪。 活 化制度是先用 0.2C活化 6次， 环境温度为 25 °C。 0.2C
活化吋， 充电电流均为 lOOmA.g-1 , 充电 6h， 放电电流为 6θΓηΑ·^， 放电截止电 位均为 1.0V。 第 6次的放电容量即为电极的初始容量 QQ。 自放电的测试方法是： 将电极按上述方法充好电后， 在 20
°C的条件下搁置 28后， 再以同样的条件放电， 所得容量为 ¾。 自放电率的计算 方法为： 自放电率= (Oo-Qi) /Q0。
[17] 从图 1可以看出， 本发明铁电极材料在 20°C下搁置 28天后
， 自放电率小于 20% , 而普通铁电极材料的自放电率约为 50%。

Claims

权利要求书
[1] 一种低自放铁电极材料， 其特征在于：
该铁电极材料由活性物质和添加剂组成。 活性物质的成分是铁或铁的化合 物。 添加剂包括： 1) 含量为 0.02 -0.15%的铟或铟的化合物，
2) 含量为 2-8%的锡或锡的化合物， 3) 含量为 1-7%的铋或铋的化合物，
4) 含量为 5-10%的石墨粉。
[2] 根据权利要求 1所述的低自放铁电极材料， 其特征在于： 活性物质可以是 Fe
304,Fe(OH)2,Fe(OH) 3，Fe203，还原铁粉， 羰基铁粉中的一种或几种。
[3] 根据权利要求 1所述的低自放铁电极材料， 其特征在于：
铟或铟的化合物包括 In、 ln203、 In2(S04)3、 In(OH)3、 InCl3 等中的一种或几种。
[4] 根据权利要求 1所述的低自放铁电极材料， 其特征在于：
锡或锡的化合物包括 Sn、 SnO、 Sn02、 SnCl2、 SnC S锡酸盐等中的一种或 几种。
[5] 根据权利要求 1所述的低自放铁电极材料， 其特征在于：
铋或铋的化合物， 包括 Bi、 Bi203、 Bi(N03)3等中的一种或几种。
[6] 根据权利要求 1所述的低自放铁电极材料， 其特征在于： 其所用的电解液为
6mol/L的 KOH水溶液， 其中加有 15g /L的 LiOH.H20。
PCT/CN2009/074716 2008-12-17 2009-10-30 低自放电铁电极材料 WO2010069209A1 (zh)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10374261B2 (en) 2011-06-15 2019-08-06 University Of Southern California High efficiency iron electrode and additives for use in rechargeable iron-based batteries
EP2951871B1 (en) * 2013-02-01 2019-08-21 Encell Technology, Inc. Iron electrode employing a polyvinyl alcohol binder
EP2951335B1 (en) * 2013-02-01 2019-08-21 Encell Technology, Inc. Coated iron electrode and method of making same
CN111146407A (zh) * 2020-02-11 2020-05-12 河南创力新能源科技股份有限公司 一种铁镍电池负极添加剂的制备方法
US11552290B2 (en) 2018-07-27 2023-01-10 Form Energy, Inc. Negative electrodes for electrochemical cells
US11611115B2 (en) 2017-12-29 2023-03-21 Form Energy, Inc. Long life sealed alkaline secondary batteries

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* Cited by examiner, † Cited by third party
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CN108511738B (zh) * 2018-06-13 2020-05-08 深圳汽航院科技有限公司 一种复合材料的制备方法、包含该复合材料的镍铁电池电极，以及镍铁电池
CN110690446A (zh) * 2019-09-29 2020-01-14 蔚蓝(广东)新能源科技有限公司 一种铁镍电池用碳包覆四氧化三铁的制备方法
CN111146431B (zh) * 2020-02-11 2022-11-29 河南创力新能源科技股份有限公司 一种铁镍电池负极复合材料及其制备方法
CN111370781A (zh) * 2020-03-16 2020-07-03 河南创力新能源科技股份有限公司 锡基化合物铁镍电池添加剂及基于该添加剂的铁镍电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5340694B1 (zh) * 1967-06-07 1978-10-28
CN1346161A (zh) * 2000-09-22 2002-04-24 潘军青 一种高铁电极及其碱性高能电池
CN1532965A (zh) * 2003-03-25 2004-09-29 勇 张 活化型铁电极

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3484291A (en) * 1968-04-19 1969-12-16 Esb Inc Gas depressor additives for iron electrodes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5340694B1 (zh) * 1967-06-07 1978-10-28
CN1346161A (zh) * 2000-09-22 2002-04-24 潘军青 一种高铁电极及其碱性高能电池
CN1532965A (zh) * 2003-03-25 2004-09-29 勇 张 活化型铁电极

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
XIANG MIN ET AL.: "Research Status on Iron Anode Used For Alkaline Battery", CHINESE BATTERY INDUSTRY, vol. 5, no. 4, August 2000 (2000-08-01), pages 172 - 173 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10374261B2 (en) 2011-06-15 2019-08-06 University Of Southern California High efficiency iron electrode and additives for use in rechargeable iron-based batteries
EP2951871B1 (en) * 2013-02-01 2019-08-21 Encell Technology, Inc. Iron electrode employing a polyvinyl alcohol binder
EP2951335B1 (en) * 2013-02-01 2019-08-21 Encell Technology, Inc. Coated iron electrode and method of making same
US11611115B2 (en) 2017-12-29 2023-03-21 Form Energy, Inc. Long life sealed alkaline secondary batteries
US11552290B2 (en) 2018-07-27 2023-01-10 Form Energy, Inc. Negative electrodes for electrochemical cells
CN111146407A (zh) * 2020-02-11 2020-05-12 河南创力新能源科技股份有限公司 一种铁镍电池负极添加剂的制备方法

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