WO2015085628A1 - 一种锌/空气电池低温启动方法 - Google Patents

一种锌/空气电池低温启动方法 Download PDF

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WO2015085628A1
WO2015085628A1 PCT/CN2013/090184 CN2013090184W WO2015085628A1 WO 2015085628 A1 WO2015085628 A1 WO 2015085628A1 CN 2013090184 W CN2013090184 W CN 2013090184W WO 2015085628 A1 WO2015085628 A1 WO 2015085628A1
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zinc
environment
air battery
battery
single cell
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French (fr)
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孙公权
燕召
王二东
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/50—Methods or arrangements for servicing or maintenance, e.g. for maintaining operating temperature
    • H01M6/5038—Heating or cooling of cells or batteries

Definitions

  • the invention relates to a method for low temperature start-up of a zinc air battery.
  • the zinc-air battery Since the positive reactant is not stored inside the battery, the zinc-air battery has a high mass-to-weight ratio energy and volume ratio energy. Among all commercial primary batteries, zinc-air batteries have the highest energy density (Journal of Power Sources 163 (2006) 591 - 597), and because of the abundant resources and low cost of zinc metal, zinc-air batteries are available in portable mobile power supplies. , large fixed power stations and other aspects have a very broad application prospects.
  • the invention aims at the above problems, and proposes that the battery is self-short-circuited inside the system, and the heat of the short-circuit reaction is used to heat the zinc-air battery, and the zinc-air battery is combined with the high-concentration KOH solution as the electrolyte, and the high-concentration KOH is proposed through the field.
  • the electrolyte method obtains a hot electrolyte and heats the battery.
  • a low-temperature starting method for a zinc air battery using a short-circuit heating method, or a chemical heating method, or a combination of the above two methods to heat a zinc-air battery in a low-temperature environment, so that the zinc-air battery can be normally started under low temperature conditions .
  • the short-circuit heating method connects the positive and negative electrodes of the zinc-air battery to realize the internal short-circuit, and heats the zinc-air battery in a low-temperature environment by the heat released by the short-circuit reaction.
  • the chemical heating method is to arrange a high concentration KOH electrolyte on site in a low temperature environment, and utilize
  • the KOH solid dissolves the released heat to heat the zinc air battery in a low temperature environment.
  • the low temperature environment of the zinc air battery is -30 ° C - (TC environment.
  • the method of the invention has the advantages of simplicity, easy implementation, no increase in the complexity of the battery structure, high energy conversion efficiency and the like.
  • Fig. 1 Output voltage curves of the single cells of Comparative Example 1 and Comparative Example 2 at a constant current discharge of 50 mA.cm- 2 .
  • Fig. 2 shows the output voltage curve of the single cell described in Example 1 at a constant current discharge of 50 mA_cm- 2 .
  • Fig. 3 is a graph showing the output voltage of the single cell of Example 2 at a constant current discharge of 50 mA 'cnr 2 .
  • Fig. 4 is a graph showing the output voltage of the single cell of Example 3 at a constant current discharge of 50 mA m- 2 .
  • Fig. 5 shows the output voltage curve of the single cell described in Example 4 at 50 mA, cnr 2 constant current discharge.
  • Fig. 6 shows the output voltage curve of the single cell described in Example 5 at a constant current discharge of 50 mA*cm- 2 .
  • FIG. 7 shows the output voltage curve of the single cell of Example 6 at a constant current discharge of 50 mA > cm- 2 .
  • Fig. 8 is a graph showing the output voltage of the single cell described in Example 7 at a constant current discharge of 50 mA_cm- 2 .
  • Fig. 9 is a graph showing the output voltage of the single cell of Example 8 at a constant current discharge of 50 mA m- 2 .
  • Figure 10 shows the output voltage curve of the single cell described in Example 9 at 50 mA, cnr 2 constant current discharge.
  • Fig. 11 shows the output voltage curve of the single cell described in Example II at 50 mA*cnr 2 constant current discharge.
  • Comparative Example 1 30.5% KOH solution was added to the zinc air battery cell electrolyte bath.
  • the single-cell cathode (Jiu Neng Jingtong (Tianjin) New Energy Technology Co., Ltd.) has an electrode area of 384 cm 2 and an anode of zinc (99.9%, Sinopharm Chemical Reagent Co., Ltd.).
  • the ratios of the cathode, anode and electrode in the subsequent comparative examples and examples are the same except for special instructions)
  • the single cell was placed in an environment of 20 ° C for more than 2 h to keep the cell and electrolyte constant with the environment. Under the condition of 50 mA, cm- 2 constant current discharge, the output voltage curve of the battery under this condition is obtained, as shown in Fig. 1. According to the output voltage curve, in a 20 ° C environment, the single cell can be normally started for 50 mA, cm- 2 constant current discharge.
  • Comparative Example 2 A 30.5% KOH solution was added to a zinc air battery cell electrolyte bath. The single cell was placed in an environment of 10 ° C for more than 2 h to keep the cell and electrolyte constant with the environment. Under the condition of 50 mA, cm- 2 constant current discharge, the output voltage curve of the battery under this condition is obtained, as shown in Fig. 1. According to the output voltage curve, in a 10 ° C environment, the single cell can be normally started for 50 mA, cm _ 2 constant current discharge.
  • Example 1 (Chemical heating method) A single cell was placed in an environment of 0 °C. 287 g of a 22% KOH solution and 35.2 g of solid KOH were placed in an environment of 0 ° C, and allowed to stand for 2 h or more to keep the KOH solution, the solid KOH, and the single cells constant with the environment. The solid KOH was added to a 22% KOH solution, and the solution was heated by the heat released during the KOH dissolution process to obtain a 30.5% KOH solution having a temperature higher than 20 °C. The obtained solution was added to a single cell and discharged at a constant current of 50 mA • cm- 2 , and the output voltage curve at startup was shown in Fig. 2.
  • the cells were placed in a 0 ° C environment and allowed to stand for more than 2 h to keep the cells and the environment at a constant temperature.
  • the single cell is started and subjected to a constant current discharge of 50 mA*cm- 2 , and the output voltage curve of the single cell is as shown in FIG. It can be seen from the discharge curve that in the environment of 0 ° C, when the method is not used, the single battery can only be maintained for about 200 seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the monomer The battery can start normally.
  • Example 2 (Chemical heating method) A single cell was placed in an environment of -10 °C. 287 g of 22% KOH solution and 35.2 g of solid KOH were placed in an environment of -10 ° C, and allowed to stand for more than 2 h to keep the KOH solution, solid KOH and single cells constant with the environment. The solid KOH was added to a 22% KOH solution, and the solution was heated by the heat released during the KOH dissolution to obtain a 30.5% KOH solution having a temperature higher than 10 °C. The obtained solution was added to a single cell and discharged at a constant current of 50 mA «cm- 2 . The output voltage curve at startup was shown in Fig. 3.
  • the cells were placed in a -10 ° C environment and allowed to stand for more than 2 h to keep the cells and environment constant.
  • the single cell is started and subjected to 50 mA*cnr 2 constant current discharge, and the output voltage curve of the single cell is shown in FIG. It can be seen from the discharge curve that in the environment of -10 ° C, when the method is not used, the single battery can only be maintained for several tens of seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the single The body battery can be started normally.
  • Example 3 (Chemical heating method) A single cell was placed in an environment of -20 °C. Take 287g 22%
  • the KOH solution and 35.2 g of solid KOH were placed in an environment of -20 ° C and allowed to stand for more than 2 h to keep the KOH solution, solid KOH and single cells constant with the environment.
  • the solid KOH was added to a 22% KOH solution, and the solution was heated by the heat released during the KOH dissolution to obtain a 30.5% KOH solution having a temperature higher than 0 °C.
  • the obtained solution was added to a single cell and discharged at a constant current of 50 mA*cm- 2 , and the output voltage curve at startup was shown in Fig. 4.
  • the cells were placed in a -20 ° C environment and allowed to stand for more than 2 h to keep the cells and the environment at a constant temperature.
  • the single cell is started and subjected to a constant current discharge of 50 mA*cm- 2 , and the output voltage curve of the single cell is as shown in FIG. It can be seen from the discharge curve that in the -20 ° C environment, when the method is not used, the single battery can only be maintained for several seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the single battery Can start normally.
  • Example 4 (Chemical heating method) A single cell was placed in an environment of -30 °C. 287 g of 22% KOH solution and 35.2 g of solid KOH were placed in an environment of -30 ° C, and allowed to stand for more than 2 h to keep the KOH solution, solid KOH and single cells constant with the environment. The solid KOH was added to a 22% KOH solution, and the solution was heated by the heat released during the KOH dissolution to obtain a 30.5% KOH solution having a temperature higher than -5 °C. The obtained solution was added to a single cell and discharged at a constant current of 50 mA*cnr 2 , and the discharge curve at the start was shown in Fig. 5. It can be seen from the discharge curve that, in the environment of -30 ° C, the single cell can be normally started by the method.
  • the cells were placed in a -30 ° C environment and allowed to stand for more than 2 h to keep the cells and environment constant.
  • the single cell is started and a 50 mA*cnr 2 constant current discharge is performed, and the single cell cannot be started.
  • Example 5 (Chemical heating method) A single cell was placed in an environment of -10 °C. 254.7 g of l2% KOH solution and 67.8 g of solid KOH were placed in an environment of -10 ° C for 2 h or more to keep the KOH solution, solid KOH and single cells constant with the environment. The solid KOH was added to a 12% KOH solution, and the solution was heated by the heat released during the KOH dissolution to obtain a 30.5% KOH solution having a temperature higher than 30 °C. This resulting solution was added to the cell, and at 50 mA * cm_ 2 constant current discharge, the discharge curve shown in Figure 6 starts.
  • the cells were placed in a -10 Torr environment and allowed to stand for more than 2 h to keep the cells constant with the environment.
  • the single cell is started and subjected to a constant current discharge of 50 mA*cm- 2 , and the output voltage curve of the single cell is as shown in FIG. 6. It can be seen from the discharge curve that in the environment of -10 ° C, when the method is not used, the single battery can only be maintained for several tens of seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the single The body battery can be started normally.
  • Example 6 (Chemical heating method) A single cell was placed in an environment of 0 °C. Take 224 mL of deionized water and 98.4 g of solid KOH, and place it in a 0 ° C environment for 2 h or more to keep the deionized water, solid KOH and single cells constant with the environment. The solid KOH is added to deionized water, and the solution is heated by the heat released during the KOH dissolution process to obtain a KOH solution having a temperature higher than 55° (: 30.5%). The obtained solution is added to the single cell, and 50 mA*cm- 2 constant current discharge,
  • the cells were placed in a 0 ° C environment and allowed to stand for more than 2 h to keep the cells and the environment at a constant temperature.
  • the single cell was started and subjected to a constant current discharge of 50 mA*cm- 2 , and the output voltage curve of the single cell was as shown in FIG. It can be seen from the discharge curve that in the environment of 0 ° C, when the method is not used, the single battery can only be maintained for about 200 seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the monomer The battery can start normally.
  • Example 7 (Short-circuit heating method) A single cell was placed in an environment of 0 °C. Add about 200mL of 30.5% KOH solution, put it in 0 ° C environment, put it for more than 2h to keep the cell and the environment constant. The single cell is directly short-circuited, and after about 10 minutes, the cell temperature can be raised from 0 ° C to above 5 ° C. The single cell is discharged at a constant current of 50 mA, cnr 2 , and the output voltage curve at startup is shown in Fig. 8.
  • the cells were placed in a 0 ° C environment and allowed to stand for more than 2 h to keep the cells and the environment at a constant temperature.
  • the single cell is started and a 50 mA* C m- 2 constant current discharge is performed.
  • the output voltage curve of the single cell is as shown in FIG. It can be seen from the discharge curve that in the environment of 0 ° C, when the method is not used, the single battery can only be maintained for about 200 seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the monomer The battery can start normally.
  • Example 8 (Short-circuit heating method) A single cell was placed in an environment of -10 °C. Add about 200mL of 30.5% KOH solution, put it in a -10 ⁇ environment, and let it stand for more than 2h to keep the cell and the environment constant. The single cell was directly short-circuited, and after about 10 min, the cell temperature rose by only about 3.6 °C. The single cell is discharged at a constant current of 50 mA*cnr 2 and the output voltage curve at startup is shown in Fig. 9.
  • the cells were placed in a -10 ° C environment and allowed to stand for more than 2 h to keep the cells and environment constant.
  • the single cell was started and subjected to 50 mA, cm- 2 constant current discharge, and the output voltage curve of the single cell was as shown in FIG. It can be seen from the discharge curve that in the environment of -10 ° C, when the method is not used, the single battery can only be maintained for several tens of seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the single The body battery can only be maintained for about 100 seconds, after which it cannot be supplied normally.
  • a zinc paste was used as the anode, see Example 9.
  • Example 9 (Short-circuit heating method) A single cell (in which the battery anode was a self-made zinc paste containing 260 g of zinc powder) was placed in an environment of -10 °C. Add about 200mL of 30.5% KOH solution, put it in the environment of -10 °C, and let it stand for more than 2h to keep the cell and the environment constant. The single cell is directly short-circuited, and after about 10 minutes, the cell temperature can be raised from -10 °C to above 10 °C. The cell at 50 mA, cm_ 2 constant current discharge, the output voltage curve of Figure 10 starts.
  • Example 10 (Short-circuit heating method) A single cell was placed in an environment of -20 °C.
  • Example 11 (Short-circuit heating method) A single cell (in which the battery anode was a self-made zinc paste, containing 260 g of zinc powder) was placed in an environment of -20 °C. Add about 200mL of 30.5% KOH solution, put it in -20 environment, put it for more than 2h to keep the cell and the environment constant. The single cell is directly short-circuited, and after about 10 minutes, the cell temperature can be raised from -20 °C to above 5 °C. The cell at 50 mA, cm_ 2 constant current discharge, the output voltage curve shown in Figure 11 during startup.
  • the same single cell was placed in a -20 ° C environment and allowed to stand for more than 2 h to keep the cell and the environment at a constant temperature.
  • the single cell was started and subjected to 50 mA, cm- 2 constant current discharge, and the output voltage curve of the single cell was as shown in FIG. It can be seen from the discharge curve that in the -20 ° C environment, when the method is not used, the single battery can only be maintained for several seconds after starting, and then the external power supply cannot be normally performed, that is, the battery cannot be normally started, and by the method, the single battery Can start normally.

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Abstract

　本发明涉及一种锌空气电池低温启动方法，包括将锌空气电池正负极相连以实现其内部短路，利用短路反应放出的热量对处于低温环境的锌空气电池加热；或于低温环境现场配置高浓度 KOH电解液，利于 KOH固体溶解放出的热量对处于低温环境的锌空气电池加热；或同时采用上述两种方法对处于低温环境的锌空气电池加热。本发明所述方法具有简便、易于实施、不增加电池结构的复杂性、能量转化效率高等优点。

Description

一种锌 /空气电池低温启动方法 技术领域
本发明涉及一种锌空气电池低温启动的方法。
背景技术
由于正极反应物不储存在电池内部， 锌空气电池拥有高的质量比能量 和体积比能量。 在所有商业化的一次电池中， 锌空气电池具有最高的能量 密度（Journal of Power Sources 163 (2006) 591 - 597)， 同时， 由于金属锌资 源丰富、 价格低廉， 因此锌空气电池在便携式移动电源、 大型固定电站等 方面均有十分广阔的应用前景。
但在低温下， 锌空气电池的放电性能急剧下降， 限制了锌空气电池在 野外极寒天气下的使用。 对于在 50 mA，cnr2电流密度下放电的锌空气电池 而言，在常温下，其可以瞬间达到输出电压大于等于 0.8 V的常规放电要求; 而在 -20°C时， 相同单体电池放电时， 在此放电要求（输出电流密度达到 50 mA，cm-2且输出电压大于等于 0.8 V) 下， 电池仅能维持数秒， 随即便无法 正常对外供电； 而在 -30°C环境下， 相同单体电池放电时无法达到输出电流 密度达到 50 mA-cm-2且输出电压大于等于 0.8 V的放电要求， 因此无法正 常对外供电。
为提高低温天气下锌空气电池的放电性能， 可利用一部分自身能量使 电池或电池系统温度升高， 使得电池或电池系统能够正常对外供电。 ZL 93232961.6和 201210352888.6等提出在电池外部加装电热器， 电池给加热 器供电产生热量并加热电池的方法， 但此方法增加了电池结构复杂性， 同 时由于加热器位于电池外部， 存在散热等使得能量利用率低的问题。 US 8071240-B2提出电池外部加装反应物储存腔， 当反应物与空气或水接触反 应时放热， 从而加热电池的方法。 但此方法增加了单体电池结构的复杂性， 且由于电池系统的紧凑型， 此方法无法在电池系统安装实施。
发明内容
本发明针对上述问题， 提出电池在系统内部自短路， 并利用短路反应 放出的热量对锌空电池加热，同时结合锌空气电池使用高浓度 KOH溶液作 为电解液的特点，提出通过现场配置高浓度 KOH电解液的方法得到热的电 解液并加热电池。 具体发明内容如下：
一种锌空气电池低温启动方法， 采用短路加热法， 或化学加热法， 或 上述两种方法结合的方法对处于低温环境的锌空气电池进行加热， 从而使 锌空气电池可以在低温条件下正常启动。
所述短路加热法为将锌空气电池正负极相连以实现其内部短路， 利用 短路反应放出的热量对处于低温环境的锌空气电池加热。
替换页 （细则第 26条 所述化学加热法为在低温环境中现场配置高浓度 KOH电解液， 利用
KOH固体溶解放出的热量对处于低温环境的锌空气电池加热。
锌空气电池所述低温环境为 -30°C-(TC的环境。
与传统方法相比， 本发明所述方法具有简便、 易于实施、 不增加电池 结构的复杂性、 能量转化效率高等优点。
附图说明
图 1 对比例 1和对比例 2所述单电池在 50 mA.cm-2恒流放电时输出电 压曲线。
图 2实施例 1所述单电池在 50 mA_cm-2恒流放电时输出电压曲线。 图 3实施例 2所述单电池在 50 mA'cnr2恒流放电时输出电压曲线。 图 4实施例 3所述单电池在 50 mA m-2恒流放电时输出电压曲线。 图 5实施例 4所述单电池在 50 mA，cnr2恒流放电时输出电压曲线。 图 6实施例 5所述单电池在 50 mA*cm-2恒流放电时输出电压曲线。 图 7实施例 6所述单电池在 50 mA>cm-2恒流放电时输出电压曲线。 图 8实施例 7所述单电池在 50 mA_cm-2恒流放电时输出电压曲线。 图 9实施例 8所述单电池在 50 mA m-2恒流放电时输出电压曲线。 图 10实施例 9所述单电池在 50 mA，cnr2恒流放电时输出电压曲线。 图 11实施例 I I所述单电池在 50 mA*cnr2恒流放电时输出电压曲线。 具体实施方式
对比例及实施例所采用的低温启动方法详见表 1。 表 1 对比例及实施例所采用的低温启动方法列表
Figure imgf000003_0001
对比例 1 : 30.5% KOH溶液加入到锌空气电池单体电池电解液槽中。 其中， 单体电池阴极 （九能京通 （天津） 新能源科技有限公司）， 电极面积 为 384 cm2, 阳极为锌片 （99.9%， 国药集团化学试剂有限公司）。 （除特殊 说明外， 后续对比例及实施例中的阴、 阳极及电极面积与此相同）
该单体电池置于 20°C环境中， 保持 2 h以上使得单体电池和电解液与 环境恒温。 在 50 mA，cm-2恒流放电条件下， 得到电池在该条件下的输出电 压曲线， 见图 1。 由输出电压曲线可知， 在 20°C环境下， 单体电池可以正 常启动进行 50 mA，cm-2恒流放电。
对比例 2:将 30.5% KOH溶液加入到锌空气电池单体电池电解液槽中。 该单体电池置于 10°C环境中， 保持 2 h以上使得单体电池和电解液与环境 恒温。 在 50 mA，cm-2恒流放电条件下， 得到电池在该条件下的输出电压曲 线， 见图 1。 由输出电压曲线可知， 在 10°C环境下， 单体电池可以正常启 动进行 50 mA，cm_2恒流放电。
实施例 1 : (化学加热法） 将单体电池置于 0°C环境中。 取 287g 22%的 KOH溶液以及 35.2g固体 KOH, 置于 0°C环境中， 放置 2h以上使 KOH溶 液、固体 KOH以及单体电池均与环境恒温。将固体 KOH加入到 22%的 KOH 溶液中， 通过 KOH溶解过程中放出的热量加热溶液， 可得到温度高于 20 °C的 30.5%的 KOH溶液。 将得到的此溶液加入到单体电池中， 并在 50 mA •cm-2恒流放电， 启动时的输出电压曲线见图 2。
为进行对比， 将单体电池置于 0°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*cm-2恒流放电， 单体电池输出电 压曲线如图 2所示。 由放电曲线可知， 在 0°C环境下， 未使用本方法时，单 体电池启动后仅能维持约 200秒， 之后便无法正常对外供电， 即电池无法 正常启动， 而通过本方法， 单体电池可以正常启动。
实施例 2: (化学加热法） 将单体电池置于 -10°C环境中。 取 287g 22% 的 KOH溶液以及 35.2g固体 KOH,置于 -10°C环境中，放置 2h以上使 KOH 溶液、 固体 KOH以及单体电池均与环境恒温。 将固体 KOH加入到 22%的 KOH溶液中， 通过 KOH溶解过程中放出的热量加热溶液， 可得到温度高 于 10°C的 30.5%的 KOH溶液。 将得到的此溶液加入到单体电池中， 并在 50 mA«cm-2恒流放电， 启动时的输出电压曲线见图 3。
为进行对比，将单体电池置于 -10°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*cnr2恒流放电， 单体电池输出电 压曲线如图 3所示。 由放电曲线可知， 在 -10°C环境下， 未使用本方法时， 单体电池启动后仅能维持数十秒， 之后便无法正常对外供电， 即电池无法 正常启动， 而通过本方法， 单体电池可以正常启动。
实施例 3 : (化学加热法） 将单体电池置于 -20°C环境中。 取 287g 22%
26 的 KOH溶液以及 35.2g固体 KOH，置于 -20°C环境中，放置 2h以上使 KOH 溶液、 固体 KOH以及单体电池均与环境恒温。 将固体 KOH加入到 22%的 KOH溶液中， 通过 KOH溶解过程中放出的热量加热溶液， 可得到温度高 于 0°C的 30.5%的 KOH溶液。 将得到的此溶液加入到单体电池中， 并在 50 mA*cm-2恒流放电， 启动时的输出电压曲线见图 4。
为进行对比，将单体电池置于 -20°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*cm-2恒流放电， 单体电池输出电 压曲线如图 4所示。 由放电曲线可知， 在 -20°C环境下， 未使用本方法时， 单体电池启动后仅能维持数秒， 之后便无法正常对外供电， 即电池无法正 常启动， 而通过本方法， 单体电池可以正常启动。
实施例 4: (化学加热法） 将单体电池置于 -30°C环境中。 取 287g 22% 的 KOH溶液以及 35.2g固体 KOH，置于 -30°C环境中，放置 2h以上使 KOH 溶液、 固体 KOH以及单体电池均与环境恒温。 将固体 KOH加入到 22%的 KOH溶液中， 通过 KOH溶解过程中放出的热量加热溶液， 可得到温度高 于 -5°C的 30.5%的 KOH溶液。 将得到的此溶液加入到单体电池中， 并在 50 mA*cnr2恒流放电， 启动时的放电曲线见图 5。 由放电曲线可知， 在 -30 °C环境下， 通过本方法， 单体电池可以正常启动。
为进行对比，将单体电池置于 -30°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*cnr2恒流放电， 单体电池无法启 动。
实施例 5: (化学加热法）将单体电池置于 -10°C环境中。 取 254.7g l2% 的 KOH溶液以及 67.8g固体 KOH，置于 -10°C环境中，放置 2h以上使 KOH 溶液、 固体 KOH以及单体电池均与环境恒温。 将固体 KOH加入到 12%的 KOH溶液中， 通过 KOH溶解过程中放出的热量加热溶液， 可得到温度高 于 30°C的 30.5%的 KOH溶液。 将得到的此溶液加入到单体电池中， 并在 50 mA*cm_2恒流放电， 启动时的放电曲线见图 6。
为进行对比，将单体电池置于 -10Ό环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*cm-2恒流放电， 单体电池输出电 压曲线如图 6所示。 由放电曲线可知， 在 -10°C环境下， 未使用本方法时， 单体电池启动后仅能维持数十秒， 之后便无法正常对外供电， 即电池无法 正常启动， 而通过本方法， 单体电池可以正常启动。
实施例 6: (化学加热法） 将单体电池置于 0°C环境中。 取 224mL去离 子水以及 98.4g固体 KOH， 置于 0°C环境中， 放置 2h以上使去离子水、 固 体 KOH以及单体电池均与环境恒温。 将固体 KOH加入到去离子水中， 通 过 KOH溶解过程中放出的热量加热溶液，可得到温度高于 55° (：的 30.5%的 KOH溶液。将得到的此溶液加入到单体电池中，并在 50 mA*cm-2恒流放电，
26 启动时的输出电压曲线见图 7。
为进行对比， 将单体电池置于 0°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*cm-2恒流放电， 单体电池输出电 压曲线如图 7所示。 由放电曲线可知， 在 0°C环境下， 未使用本方法时，单 体电池启动后仅能维持约 200秒， 之后便无法正常对外供电， 即电池无法 正常启动， 而通过本方法， 单体电池可以正常启动。
实施例 7: (短路加热法） 将单体电池置于 0°C环境中。 加入约 200mL 30.5%的 KOH溶液，置于 0°C环境中，放置 2h以上使单体电池与环境恒温。 将单体电池直接短路，约 lOmin后，单体电池温度可从 0°C升高至 5°C以上。 将单体电池在 50 mA，cnr2恒流放电， 启动时的输出电压曲线见图 8。
为进行对比， 将单体电池置于 0°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA*Cm-2恒流放电， 单体电池输出电 压曲线如图 8所示。 由放电曲线可知， 在 0°C环境下， 未使用本方法时，单 体电池启动后仅能维持约 200秒， 之后便无法正常对外供电， 即电池无法 正常启动， 而通过本方法， 单体电池可以正常启动。
实施例 8: (短路加热法）将单体电池置于 -10°C环境中。 加入约 200mL 30.5%的 KOH溶液， 置于 -10Ό环境中， 放置 2h以上使单体电池与环境恒 温。 将单体电池直接短路， 约 lOmin后， 单体电池温度仅升高约 3.6°C。将 单体电池在 50 mA*cnr2恒流放电， 启动时的输出电压曲线见图 9。
为进行对比，将单体电池置于 -10°C环境中并放置 2h以上使单体电池与 环境恒温。 对单体电池启动并进行 50 mA，cm-2恒流放电， 单体电池输出电 压曲线如图 9所示。 由放电曲线可知， 在 -10°C环境下， 未使用本方法时， 单体电池启动后仅能维持数十秒， 之后便无法正常对外供电， 即电池无法 正常启动， 而通过本方法， 单体电池也仅能维持约 100秒， 之后便无法正 常对外供电。 为改善短路加热法低温启动性能， 改用锌膏为阳极， 见实施 例 9。
实施例 9: (短路加热法） 将单体电池 （其中电池阳极为自制锌膏， 含 锌粉 260g) 置于 -10°C环境中。 加入约 200mL 30.5%的 KOH溶液， 置于 -10 °C环境中， 放置 2h以上使单体电池与环境恒温。 将单体电池直接短路，约 lOmin后， 单体电池温度可从 -10 °C升高至 10 °C以上。 将单体电池在 50 mA，cm_2恒流放电， 启动时的输出电压曲线见图 10。
为进行对比，将上述同样单体电池置于 -10'C环境中并放置 2h以上使单 体电池与环境恒温。 对单体电池启动并进行 50 mA*cm-2恒流放电， 单体电 池输出电压曲线如图 10所示。 由放电曲线可知， 在 -10°C环境下， 未使用本 方法时， 单体电池启动后仅能维持数十秒， 之后便无法正常对外供电， 即 电池无法正常启动， 而通过本方法， 单体电池可以正常启动。 实施例 10: (短路加热法）将单体电池置于 -20°C环境中。加入约 200mL 30.5%的 KOH溶液， 置于 -20°C环境中， 放置 2h以上使单体电池与环境恒 温。 将单体电池直接短路， 约 lOmin后， 单体电池温度仅升高 1.3 °C。 单体 电池无法启动进行 50 mA*cm-2恒流放电。为改善短路加热法低温启动性能， 改用锌膏阳极， 见实施例 11。
实施例 11 : (短路加热法） 将单体电池 （其中电池阳极为自制锌膏，含 锌粉 260g)置于 -20°C环境中。 加入约 200mL 30.5%的 KOH溶液， 置于 -20 环境中， 放置 2h以上使单体电池与环境恒温。 将单体电池直接短路，约 lOmin后， 单体电池温度可从 -20 °C升高至 5 °C以上。 将单体电池在 50 mA，cm_2恒流放电， 启动时的输出电压曲线见图 11。
为进行对比，将上述同样单体电池置于 -20°C环境中并放置 2h以上使单 体电池与环境恒温。 对单体电池启动并进行 50 mA，cm-2恒流放电， 单体电 池输出电压曲线如图 11所示。 由放电曲线可知， 在 -20°C环境下， 未使用本 方法时， 单体电池启动后仅能维持数秒， 之后便无法正常对外供电， 即电 池无法正常启动， 而通过本方法， 单体电池可以正常启动。

Claims

1.一种锌空气电池低温启动方法， 其特征在于. - 采用短路加热法， 或化学加热法， 或上述两种方法结合的方法对处于 低温环境的锌空气电池进行加热， 从而使锌空气电池可以在低温条件下正 常启动。
2.如权利要求 1所述锌空气电池低温启动方法， 其特征在于： 所述短路加热法为将锌空气电池正负极相连以实现其内部短路， 利用 短路反应放出的热量对处于低温环境的锌空气电池加热。
3.如权利要求 1所述锌空气电池低温启动方法， 其特征在于： 所述化学加热法为在低温环境中现场配置浓度为 20%-50%的 KOH电 解液， 将电解液注入锌空气电池的电解液腔中， 利用 KOH固体溶解放出的 热量对处于低温环境的锌空气电池加热。
4.如权利要求 1、 2或 3所述锌空气电池低温启动方法， 其特征在于： 锌空气电池所述低温环境为 -30 °C -0 °C的环境。
替换页 （细则第 26条)
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