Article(id=1190684595642315757, tenantId=1146029695717560320, journalId=1189987059142926344, issueId=1190684594115589101, articleNumber=null, orderNo=null, doi=10.19457/j.1001-2095.dqcd25719, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1711209600000, receivedDateStr=2024-03-24, revisedDate=1713715200000, revisedDateStr=2024-04-22, acceptedDate=null, acceptedDateStr=null, onlineDate=1761810929450, onlineDateStr=2025-10-30, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1761810929450, onlineIssueDateStr=2025-10-30, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1761810929450, creator=13701087609, updateTime=1761810929450, updator=13701087609, issue=Issue{id=1190684594115589101, tenantId=1146029695717560320, journalId=1189987059142926344, year='2025', volume='55', issue='4', pageStart='3', pageEnd='96', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1761810929087, creator=13701087609, updateTime=1761811258832, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1190685977225081530, tenantId=1146029695717560320, journalId=1189987059142926344, issueId=1190684594115589101, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1190685977225081531, tenantId=1146029695717560320, journalId=1189987059142926344, issueId=1190684594115589101, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=33, endPage=40, ext={EN=ArticleExt(id=1190684595914945520, articleId=1190684595642315757, tenantId=1146029695717560320, journalId=1189987059142926344, language=EN, title=Energy Efficiency Modeling and Optimization of Aluminum Air Battery Based on Internal Resistance Characteristics, columnId=null, journalTitle=Electric Drive, columnName=null, runingTitle=null, highlight=null, articleAbstract=

In order to reduce the loss of electric energy in the process of energy conversion and improve the energy efficiency of aluminum air battery,an energy efficiency model based on the internal resistance characteristics of aluminum air battery was established,and the variations of operating conditions (operating temperature,electrolyte concentration),internal resistance characteristics,output characteristics and energy efficiency were studied. In order to improve the energy efficiency of aluminum air battery,an improved pollination algorithm was adopted to obtain the optimal working temperature and electrolyte concentration under constant current density output. The validity of the model and method was verified by simulation and experiment. The results show that the energy efficiency can be improved by co-optimizing the operation conditions,and the total internal resistance can be reduced and the output performance can be improved by increasing the energy efficiency.

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为降低能量转换过程中的电能损耗,提高铝空气电池能量效率,建立基于内阻特性的铝空气电池能量效率模型。研究操作条件(工作温度、电解液浓度)、内阻特性、输出特性与能量效率之间的变化规律;并以能量效率最大为优化目标,采用改进花授粉算法,获得恒定电流密度输出下的最优工作温度和电解液浓度,实现铝空气电池能量效率的提高;通过仿真和实验验证模型及方法的有效性。研究结果表明:通过协同优化铝空气电池的操作条件,能够提高能量效率;提高铝空气电池能量效率能够降低总内阻,改善输出性能。

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向志平(1997—),男,硕士研究生,主要研究方向为铝空气电池性能优化方向,Email:

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向志平(1997—),男,硕士研究生,主要研究方向为铝空气电池性能优化方向,Email:

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journalId=1189987059142926344, articleId=1190684595642315757, language=CN, orderNo=5, keyword=输出特性)], refs=[Reference(id=1191113179938832997, tenantId=1146029695717560320, journalId=1189987059142926344, articleId=1190684595642315757, doi=null, pmid=null, pmcid=null, year=2023, volume=53, issue=5, pageStart=568, pageEnd=571, url=null, language=null, rfNumber=[1], rfOrder=0, authorNames=朱奎, 韩基泰, 李昊, journalName=电池, refType=null, unstructuredReference=朱奎, 韩基泰, 李昊. 铝空气电池固态和准固态电解质研究进展[J]. 电池, 2023, 53(5):568-571., articleTitle=铝空气电池固态和准固态电解质研究进展, refAbstract=null), Reference(id=1191113180010136166, tenantId=1146029695717560320, journalId=1189987059142926344, articleId=1190684595642315757, doi=null, pmid=null, pmcid=null, year=2023, volume=53, issue=5, pageStart=568, pageEnd=571, url=null, language=null, rfNumber=[1], rfOrder=1, authorNames=ZHU K, HAN J T, LI H, journalName=Battery Bimonthly, refType=null, unstructuredReference=ZHU K, HAN J T, LI H. 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different working conditions, figureFileSmall=8k1DBw27Wa+hb9eqzRkA8g==, figureFileBig=UEywQi5dF3jFC7CCnDjb4g==, tableContent=null), ArticleFig(id=1191113178248528479, tenantId=1146029695717560320, journalId=1189987059142926344, articleId=1190684595642315757, language=CN, label=图7, caption=不同工作工作状态下铝空气电池电化学交流阻抗图谱, figureFileSmall=8k1DBw27Wa+hb9eqzRkA8g==, figureFileBig=UEywQi5dF3jFC7CCnDjb4g==, tableContent=null), ArticleFig(id=1191113178365968992, tenantId=1146029695717560320, journalId=1189987059142926344, articleId=1190684595642315757, language=EN, label=Tab.1, caption=

Model simulation parameter table

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参数 数值 参数 数值 参数 数值
T 295~345 K S 1 cm2 n 4
c 2~8 mol·L-1 L 1 cm a 0.8
i 0~300 mA·cm-2 Relect 0.6 Ω·cm2 t 2 h
δ 100 μm p 0.21 atm α 0.15
Ea 5.314 J/(mol·K) mlea 0.1 mg·h-1 r 1.09
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模型仿真参数表

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参数 数值 参数 数值 参数 数值
T 295~345 K S 1 cm2 n 4
c 2~8 mol·L-1 L 1 cm a 0.8
i 0~300 mA·cm-2 Relect 0.6 Ω·cm2 t 2 h
δ 100 μm p 0.21 atm α 0.15
Ea 5.314 J/(mol·K) mlea 0.1 mg·h-1 r 1.09
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Comparison of optimization results before and after improvement of pollination algorithm

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i/mA·cm-2 改进花授粉算法 标准花授粉算法
T/K c/(mol·L-1 ε/% T/K c/(mol·L-1 ε/%
50 326.2 7.0 18.32 325.7 7.2 17.55
90 328.4 6.8 31.25 329.2 6.3 29.39
130 330.2 6.6 36.23 329.7 6.3 35.16
170 331.3 6.4 39.68 331.7 6.5 38.59
210 332.0 6.1 41.35 331.5 6.2 40.59
250 329.6 5.8 37.57 330.4 5.3 36.25
290 319.4 5.3 22.35 321.5 4.7 20.77
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花授粉算法改进前后优化结果对比

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i/mA·cm-2 改进花授粉算法 标准花授粉算法
T/K c/(mol·L-1 ε/% T/K c/(mol·L-1 ε/%
50 326.2 7.0 18.32 325.7 7.2 17.55
90 328.4 6.8 31.25 329.2 6.3 29.39
130 330.2 6.6 36.23 329.7 6.3 35.16
170 331.3 6.4 39.68 331.7 6.5 38.59
210 332.0 6.1 41.35 331.5 6.2 40.59
250 329.6 5.8 37.57 330.4 5.3 36.25
290 319.4 5.3 22.35 321.5 4.7 20.77
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基于内阻特性的铝空气电池能量效率建模与优化
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向志平 1 , 马玉河 1 , 高剑 2
电气传动 | 综合能源与现代电网 2025,55(4): 33-40
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电气传动 | 综合能源与现代电网 2025, 55(4): 33-40
基于内阻特性的铝空气电池能量效率建模与优化
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向志平1 , 马玉河1, 高剑2
作者信息
  • 1 中国计量大学 机电工程学院,浙江 杭州 310018
  • 2 华能国际电力江苏能源开发有限公司 清洁能源分公司,江苏 南京 210015
  • 向志平(1997—),男,硕士研究生,主要研究方向为铝空气电池性能优化方向,Email:

Energy Efficiency Modeling and Optimization of Aluminum Air Battery Based on Internal Resistance Characteristics
Zhiping XIANG1 , Yuhe MA1, Jian GAO2
Affiliations
  • 1 College of Mechanical and Electrical Engineering,China Jiliang University,Hangzhou 310018,Zhejiang,China
  • 2 Clean Energy Branch,Huaneng International Power Jiangsu Energy Development Co.,Ltd.,Nanjing 210015,Jiangsu,China
出版时间: 2025-04-20 doi: 10.19457/j.1001-2095.dqcd25719
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为降低能量转换过程中的电能损耗,提高铝空气电池能量效率,建立基于内阻特性的铝空气电池能量效率模型。研究操作条件(工作温度、电解液浓度)、内阻特性、输出特性与能量效率之间的变化规律;并以能量效率最大为优化目标,采用改进花授粉算法,获得恒定电流密度输出下的最优工作温度和电解液浓度,实现铝空气电池能量效率的提高;通过仿真和实验验证模型及方法的有效性。研究结果表明:通过协同优化铝空气电池的操作条件,能够提高能量效率;提高铝空气电池能量效率能够降低总内阻,改善输出性能。

铝空气电池  /  能量效率  /  性能优化  /  内阻特性  /  输出特性

In order to reduce the loss of electric energy in the process of energy conversion and improve the energy efficiency of aluminum air battery,an energy efficiency model based on the internal resistance characteristics of aluminum air battery was established,and the variations of operating conditions (operating temperature,electrolyte concentration),internal resistance characteristics,output characteristics and energy efficiency were studied. In order to improve the energy efficiency of aluminum air battery,an improved pollination algorithm was adopted to obtain the optimal working temperature and electrolyte concentration under constant current density output. The validity of the model and method was verified by simulation and experiment. The results show that the energy efficiency can be improved by co-optimizing the operation conditions,and the total internal resistance can be reduced and the output performance can be improved by increasing the energy efficiency.

aluminum air battery  /  energy efficiency  /  performance optimization  /  internal resistance characteristics  /  output characteristics
向志平, 马玉河, 高剑. 基于内阻特性的铝空气电池能量效率建模与优化. 电气传动, 2025 , 55 (4) : 33 -40 . DOI: 10.19457/j.1001-2095.dqcd25719
Zhiping XIANG, Yuhe MA, Jian GAO. Energy Efficiency Modeling and Optimization of Aluminum Air Battery Based on Internal Resistance Characteristics[J]. Electric Drive, 2025 , 55 (4) : 33 -40 . DOI: 10.19457/j.1001-2095.dqcd25719
为了缓解日益严重的能源危机和环境污染问题,开发非化石能源是一项迫在眉睫的任务。铝空气电池作为一种清洁能源,具有比能量高、安全环保等优势,广泛应用于应急能源和水下供电设备。然而,在电池实际运行过程中存在能量效率低的问题。因此研究提高能量效率的方法是铝空气电池研究的大势所趋[1]
近年来,专家学者对铝空气电池能量效率优化均是通过改善电极结构和更改电解液种类两个方面实现。在改善电极结构方面,文献[2-5]通过研究铝空气电池的自腐蚀现象和能量效率,证实阳极含有锑、锰、铟等元素的铝空气电池,具有更高的阳极利用率和能量效率。文献[6]设计一种含有碳纤维、纤维素和活性碳粉的阴极活性碳片,利用活性炭孔隙率大、比表面积大的特点,提升阴极性能,实现能量密度和能量效率的提高。文献[7]将铝空气电池的阳极采用网格封装,实现能量的合理分配,进而提高电池的能量效率。文献[8]通过研究铝空气电池的电极间距、电解液流速和进气压力等因素对输出性能和能量效率的影响作用和变化规律,进而实现优化控制,提高电池能量效率。在更改电解液种类方面,文献[9-12]设计一种含有聚乙烯醇、葡萄糖、菊花冠叶提取物、甘油等添加剂的电解液,进而降低铝阳极的自腐蚀速率,改善电池输出性能,提高能量效率。文献[13-14]设计一种具有酸-碱混合电解液的铝空气电池,提高溶液电导率,实现电池的输出性能和能量效率显著提升。文献[15]设计一种乙酸钾-氢氧化钾混合电解液的高效碱性铝空气电池,使得能量转换过程中的阳极自腐蚀现象得到抑制,实现电池的放电容量和能量效率的提高。文献[16]通过构建一种新型准固态电解质,利用其均匀的孔隙结构和丰富的亲水性,抑制铝阳极的自腐蚀现象,实现铝空气电池能量效率的提高。
铝空气电池能量转换过程中,电池结构(电极结构、电解液种类等)和操作条件(工作温度和电解液浓度)是影响电池能量效率的重要因素。电池结构是铝空气电池的固有属性,在设计制造阶段确定。然而,在工程应用中操作条件是影响能量效率的可控因素。因此,本文建立基于内阻特性的铝空气电池能量效率模型,研究操作条件对能量效率的影响作用和变化规律;通过改进花授粉算法获得恒定电流密度输出下,能量效率最大时的最优工作温度和电解液浓度,实现能量效率的提高;利用恒流放电实验和交流阻抗特性实验,验证了方法的有效性。该优化方法具有一定的工程实用价值。
铝空气电池的能量效率ε代表电池将金属铝中存储的化学能转换为输出电能的能力,如下式所示:
ε = W W 0 × 100 % = U i S t / Δ m W 0 × 100 % = U i S / m A l W 0 × 100 %
式中:W为实际能量密度,mW·h·g-1W0为理论能量密度,值为8 100 mW·h·g-1U为输出电压,V;i为电流密度,mA·cm-2 Δm为阳极质量损耗,g;t为放电时间,h;S为有效反应面积,cm2mAl为铝耗速率,g·h-1
铝空气电池通过铝阳极的氧化还原反应将化学能转换为输出电能,从而实现能量转换。然而在能量转换过程中存在自腐蚀现象,使得所消耗的铝阳极不能完全转换为电能,且自腐蚀现象与电流密度、工作温度和电解液浓度相关。因此,铝空气电池铝耗速率mAl如下式所示:
$m_{\mathrm{Al}}=M_{\mathrm{Al}} \frac{i S}{z F}\left[1+\frac{E_{\mathrm{a}}\left(T-T_{0}\right)}{R T_{0}}+r \cdot \ln \left(\frac{C_{\mathrm{Al}^{-}}}{C_{0}}\right)\right]+m_{\text {lea }}$
式中:MAl为铝的摩尔质量,g·mol-1F为法拉第常数;z为电子转移数;Ea为与温度相关的摩尔比热容,J/(mol·K);TT0分别为实际工作温度和标准工作温度,K;R为理想气体常数;r为电池反应随电解液浓度变化的速率常数;mlea为闲置损耗速率,表征电池未放电时的自然损耗速率,g·h-1C0为参考电解液浓度,mol·L-1 C A l 为电解液中所含铝元素的离子化合物浓度。
C A l 近似于反应物总浓度Cg的0.36倍,Cg计算如下式:
C g = 10 β 7 + β 8 T c H T , 0 e x p [ β 9 ( 1 / T 0 1 / T ) ] p
式中:HT,0为亨利常数,mol·L-1·atm-1βi为模型仿真参数;p为参与反应的氧气分压,atm。
根据铝空气电池电化学反应理论基础,建立二阶RC等效电路,如图1所示。图中,Eocv为开路电压;Rf,Rm,Rd分别为活化内阻、欧姆内阻、浓差内阻[17];C1,C2为双层电容。
图1可知,内阻特性是造成输出电压U低于开路电压的根本原因,则输出电压U可用下式表示:
U = E o c v i R c e l l = E o c v i ( R f + R m + R d )
其中
R f = R T α n F i A l n { p 0 T 0 i A / { i 0 p T e x p [ Δ + G / R ( 1 / T 0 1 / T ) ] } } R m = L a ( β 1 c + β 2 c 2 + β 3 c T + β 4 c T + β 5 c 3 + β 6 c 2 T 2 ) + N R e l e c t R d = R T δ C g τ ( n F ) 2 D e f f
其中
τ = e x p ( β 10 δ n F C g D e f f i A ) D e f f = D 0 e x p [ Δ + G R ( 1 T 0 1 T ) ] ε 0 1.5
式中:Rcell为电池总内阻,Ω∙cm2iAi0分别为电流密度和交换电流密度,A·cm-2αn分别为电荷转移系数和转移电荷数;Δ+G为电化学反应活化能,J·mol-1c为电解液浓度,mol·L-1L为电极间距,cm;a为电导率修正因子;Relect为电极等效欧姆电阻,Ω·cm2δ为扩散层厚度,μm;τ为电流密度相关因子;Deff为有效扩散率,m2·s-1
综上可得铝空气能量效率ε模型如下:
ε = [ E o c v i ( R f + R m + R d ) ] i S × 100 % W 0 { M A l i S z F 1 E a ( T T 0 ) R T 0 + r l n ( C A l C 0 ) ] + m l e a }
铝空气电池的能量效率反映电池内部能量转换的能力大小,能量转换过程受操作条件(电池工作温度和电解液浓度)的直接影响[8]。适宜的操作条件使电池的能量转换能力增大,输出性能提升,能量效率提高。针对第1节建立的能量效率模型,研究操作条件、内阻特性和输出特性与能量效率之间的变化规律,获得影响铝空气电池能量效率的反应机理,对优化电池输出性能、提高能量效率有重要意义。表1为模型仿真参数。
铝空气电池的能量效率是内阻特性(总内阻Rcell)改变的外部反映,操作条件是影响内阻特性的决定性因素。仿真分析操作条件和内阻特性对铝空气电池能量效率的影响作用,研究影响铝空气电池能量效率的本质原因,仿真结果如图2所示。
图2分析可知,能量效率随电流密度的增大先增大后减小,总内阻则与之相反。低电流密度段,活化内阻主导,电流密度增大,电化学反应速率加快,活化内阻和总内阻减小,电能损耗减小,能量效率提高;中电流密度段,欧姆内阻主导,电流密度的改变不对欧姆内阻产生影响,总内阻变化极微,能量效率随着电流密度的增大而增大;高电流密度段,浓差内阻主导,电流密度增大,溶氧速度不满足电化学反应速率,导致空气电极的浓差梯度增大,催化层界面的反应物浓度减小,浓差内阻和总内阻增大,能量效率减小。
图2a分析可知:①低电流密度段,电池处于反应初期,需克服活化能垒,活化内阻较大,较高的温度可以增加催化剂的反应面积和活性,降低活化内阻,减小电能损耗,提高能量效率;②中电流密度段,欧姆内阻主导,提升温度有助于增大溶液电导率,提升氧气扩散率,从而减小总内阻和电能损耗,提高能量效率,但过高的温度会导致自腐蚀现象加剧,电解液溶液蒸发,使总内阻增大,能量效率降低;③高电流密度段,浓差内阻主导,适当提升温度有助于提高氧的溶解度,减小总内阻,但温度过高会使自腐蚀现象加剧,空气电极退化,且使氧气溶解度下降,导致浓差极化现象加重,能量效率降低。
图2b分析可知,由于活化内阻不受电解液浓度的影响,低电流密度段,维持较高的电解液浓度可以提高电解液的电导率并维持反应物供给,降低欧姆内阻和浓差内阻,减小电池内部损耗,提高能量效率。在中高电流密度段,适当提升浓度有助于增大溶液电导率,增加反应物供给,减小总内阻,提升能量效率,浓度过高会导致电解液析出,自由离子对减少,抑制氧还原反应,且使氧气溶解度下降,降低能量效率。
综上可知,恒定电流密度输出下,协同优化控制电池内部工作温度和电解液浓度,可以减小总内阻,提高能量效率。
能量效率是评价铝空气电池输出性能的重要指标,研究影响铝空气电池输出性能的反应机理,分析操作条件、输出性能与能量效率之间的变化规律,是确定最佳操作条件和实现能量效率优化控制的前提,仿真结果如图3所示。
图3分析可知:①低电流密度段,活化内阻影响较大,随着电流密度的上升,活化内阻和总内阻迅速减小,输出电压下降较快;恒定电流密度输出时,提高电池工作温度可以减小活化损耗,输出电压增大,提高能量效率,电解液浓度对活化内阻无影响,能量效率变化不明显。②中电流密度段,欧姆内阻占主导,电流密度的变化对欧姆内阻无影响,输出电压随电流密度上升线性减小;恒定电流密度输出时,温度和电解液浓度过低会导致溶液离子传输能力过小,欧姆内阻增大,温度过高,电解液蒸发变得粘稠,影响离子传输能力,电解液浓度过高,电解液溶质析出,导致电导率下降。故适当提高工作温度和电解液浓度可以降低电池的欧姆内阻,减少欧姆损耗,输出电压增大,能量效率提高。低中电流密度段,输出电压下降的速度不及电流密度上升的速度,能量效率整体呈现上升趋势。③高电流密度段,浓差内阻占主导,电化学反应速率较快,反应产物增多,浓差极化现象加重,输出电压随电流密度上升,下降速度变快;恒定电流密度输出时,工作温度过高,会导致铝阳极副反应加剧、空气电极退化、氧气溶解度下降,维持适中的温度有助于减小浓差内阻和总内阻,从而减小电压损失,提高能量效率。电解液浓度过高,会导致氧还原反应被抑制、氧气溶解度下降、固体产物更易析出,维持适中的浓度有助于减小电压损失,提高能量效率。高电流密度段,因浓差极化现象,使得电流密度上升的速度不及输出电压下降的速度,能量效率呈现出下降的趋势。
综上可知,不同电流密度输出时,适宜的操作条件可以实现输出性能优化,能量效率提高。
本文所研究的铝空气电池能量效率优化问题,是一种搜索空间复杂的非线性优化问题,可使用差分进化算法、粒子群算法、遗传算法、花授粉算法等智能优化算法。由于标准算法缺乏一定的自适应性,局部搜索能力弱,易陷入局部最优。本文使用改进的花授粉算法,实现铝空气电池能量效率优化求解。
标准花授粉算法的核心原则包含:①生物异花授粉行为,通过Levy函数实现全局搜索;②非生物自花授粉行为,进行局部搜索;③繁衍概率与参与授粉的两朵花的相似度成比例;④转换概率p∈[0,1],控制两种授粉模式之间的转换[18]
标准花授粉算法中由于Levy函数的引入,使得算法在一定程度上避免个体陷入局部最优,但是算法缺乏自适应性。改进花授粉算法通过增加一个随迭代次数改变的动态权重ω,使异花授粉行为具有一定的自适应性。动态权重ω如下式所示:
ω = ω m a x ( ω m a x ω m i n ) k / M T
式中:ωmaxωmin分别为最大权重值和最小权重值;MT为最大迭代次数;k为当前迭代次数。
改进后的异花授粉行为如下式所示:
x i k + 1 = x i k + ω L ( λ ) ( x i k g k )
其中
L ( λ ) λ Γ ( λ ) s i n ( π θ / 2 ) π 1 s 1 + λ s s 0 0
式中:x为当前个体; x i k + 1k+1次迭代的个体; g k为当前种群迭代中的全局最优个体;Lλ)为Levy函数。
标准花授粉算法中,自花授粉行为的位置更新由随机抽取的两个个体决定,在搜索最优解的过程中具有盲目性和不定向性。本文将历史全局最优个体引入到自花授粉行为,使得位置更新具有定向性,如下式所示:
x i k + 1 = x b e s t k + γ ( x j k x i k )
式中: x b e s t k为历史全局最优个体;γ∈[0,1]; x j k为当前种群迭代中的随机个体。
设置最大迭代次数MT为1 000;种群数为50;转换概率p为0.1;ωmax为0.95,ωmin为0.35;γ为[0,1]内的随机数;将铝空气电池能量效率模型作为适应度函数,如式(7)所示,采用花授粉算法,获得不同电流密度输出下,能量效率最大时的操作条件,算法优化求解流程如图4所示。改进前后花授粉算法求解得出的优化结果如表2所示。
表2分析可知:1)恒定电流密度输出下,改进花授粉算法寻优所得的能量效率高于标准花授粉算法寻优结果,表明改进花授粉算法的搜索能力更强,准确性更高。2)最大能量效率随着电流密度的增大,呈现先增大后减小的趋势。这是由于能量转换过程初期,电化学反应速率较慢,电池内部电能损耗较大,电池将化学能转换为输出电能的能力较弱,能量效率较低。随着电流密度的增大,电化学反应速率加快,电池内部电能损耗逐渐减小,能量效率逐渐增大,当电池处于中电流密度段时,电池将化学能转换为电能的能力达到顶峰,此时电流密度继续增加,因浓差极化现象的影响,导致电池将化学能转化为输出电能的能力下降,能量效率降低[19]。3)最优工作温度随着电流密度的增大呈现先增大后减小的变化趋势。低电流密度段,适当升高温度可以减小电池总内阻,降低电池自身的损耗,故低电流密度下,最优工作温度应逐渐升高;中电流密度段,提高温度对主反应具有促进作用,可以降低电池总内阻,减少电能损耗,但随着电流密度的上升,能量转换过程释放大量的热,导致电解液蒸发,需逐渐降低温度。故中电流密度下,最优工作温度应先增后减;高电流密度时,自腐蚀现象和浓差现象显著,温度过高会加剧自腐蚀现象和浓差现象,导致铝阳极的浪费和电能损耗增大,因此高电流密度下,最优工作温度应逐渐降低。4)最优电解液浓度随着电流密度的增大呈现逐渐减小的变化趋势。这是由于随着电流密度的增大,电解液浓度过高会增强自腐蚀现象,导致铝阳极的浪费,加剧浓差极化现象的发生[20],电能损耗增多,能量效率降低,因此随着电流密度的增大,最优电解液浓度逐渐减小。
本节开展铝空气电池能量效率优化实验,获得不同电流密度、不同操作条件下的恒流放电实验和交流阻抗特性实验结果。实验系统主要包括铝空气电池、直流电子负载(KIKUSUI PLZ1004W)、交流阻抗测试仪(KIKUSUI KMF2150)、恒温水浴槽、温度传感器、工控机、高精度电子秤(FA1004C-2004CS)以及电解液浓度检测装置(DDSJ-319L)。实验系统如图5所示。
通过设置直流电子负载为恒流输出模式,在不同电流密度下,对铝空气电池进行1 h的恒流放电实验,分别测量放电前、后阳极铝板质量,获得阳极质量损耗Δm以及电池在稳定输出时的输出电压U。实验过程中,优化状态对应工作在最优操作条件下(表2)的铝空气电池状态;正常状态指铝空气电池未经优化操作的状态,采用电池制造商建议范围内的电池工作温度和电解液浓度,为避免实验结果的片面性,将正常状态划分为正常状态1和正常状态2,分别表示操作条件向下偏离和向上偏离最优操作条件时(电池工作温度T偏离10 K,电解液浓度c偏离1 mol·L-1)的铝空气电池状态。采用式(1)计算铝空气电池的能量效率,获得实验数据,采用式(4)和式(7)计算获得仿真数据。实验结果如图6所示(点和点线为实验结果,线为仿真结果)。
图6可知:1)随着电流密度的增大,优化状态和正常状态下的铝空气电池输出电压均逐渐减小。这是由于随着电池电化学反应的进行,电极表面反应物浓度逐渐减小,导致输出电压逐渐减小[21]。2)随着电流密度的增大,阳极损耗量逐渐增多。这是由于随着电流密度的增大,电池内部的电化学反应加剧,铝耗速率逐渐加快,因此铝空气电池在1 h放电后所消耗的阳极损耗量逐渐增多。3)随着电流密度的增大,各工作状态下的能量效率先增大后减小。这是由于随着电流密度的增大,电池总内阻先减后增,电池内部的损耗先减后增,导致能量效率先增后减。4)相较于正常状态,恒定电流密度输出下,电池工作在优化状态(改进)时,铝空气电池输出电压和能量效率明显提升,输出电压提升范围为0.23~0.49 V,能量效率提升范围为1.88%~16.06%;仿真结果与实验结果规律一致且拟合度较高,表明模型和方法的有效性。
在不同电流密度、不同工作状态下对铝空气电池进行交流阻抗特性实验。利用交流阻抗测试仪向实验系统发射0.1 Hz~20 kHz的交流信号,获得实验曲线。根据二阶RC等效电路模型,建立如下式所示的交流阻抗特性模型:
Z = R m + R f + R d + j ω R f R d C 2 j ω C 1 ( R f + R d + R f R d j ω C 2 ) + j ω R d C 2 + 1
图7为铝空气电池在电流密度i为50 mA·cm-2,130 mA·cm-2,250 mA·cm-2时的电化学交流阻抗图谱(点为实验部分,线为仿真部分)。实验所获得的电化学交流阻抗图谱包含低频弧和高频弧两部分圆弧。其中,曲线的起始点为高频响应点,代表欧姆内阻Rm,曲线的终点为低频响应点,代表电池总内阻Rcell,高频弧半径的大小主要受活化内阻Rf影响,低频弧半径大小主要受浓差内阻Rd影响,欧姆内阻和总内阻的增大分别导致曲线起始点和终点向坐标轴右侧移动,活化内阻和浓差内阻的增大分别导致高频弧和低频弧半径增大。
图7可知:1)优化状态(改进)下,电池总内阻最小,且相较于正常状态总内阻明显减小,减小范围为0.698 5~2.307 Ω·cm2。这是由于当电池工作在优化状态(改进)时,电池的能量效率最大,由电池自身损耗的电能最少,表现为电池总内阻最小。2)随着电流密度的上升,各状态下,电池总内阻先减小后增大。这是由于电池自身的损耗先减小后增大,能量效率随电流密度先增大后减小。3)仿真曲线与实验曲线规律一致且拟合度较高,表明模型有效可靠。4)低电流密度输出时,铝空气电池的曲线呈现单弧形式,低频弧几乎不存在。这是由于低电流密度输出时,电池总内阻由活化内阻主导,浓差内阻极小。5)中电流密度输出时,铝空气电池的曲线呈现高频弧大、低频弧小的曲线特征。这是由于中电流密度输出时,电池总内阻由欧姆内阻主导,此时浓差现象开始显现,浓差内阻较小。6)高电流密度输出时,铝空气电池的曲线呈现高频弧小、低频弧大的曲线特征。这是由于高电流密度输出时,电池总内阻由浓差内阻主导,此时浓差现象显著,浓差内阻较大。
本文建立铝空气电池能量效率模型,通过仿真与实验,研究操作条件、内阻特性、输出特性与能量效率之间的变化规律,并以能量效率最大为优化目标,采用改进花授粉算法求解得到最优操作条件,获得如下结论:
1)协同优化铝空气电池操作条件,可以减小总内阻,改善电池输出特性,提高能量效率。
2)以能量效率最大为优化目标,采用改进花授粉算法,获得最优操作条件,实现铝空气电池能量效率的优化,该方法有效可靠。
3)通过铝空气电池恒流放电和交流阻抗特性实验,证实工作在最优操作条件下,电池总内阻减小,输出性能和能量效率整体提高,总内阻减小范围为0.698 5~2.307 Ω·cm2,输出电压提升范围为0.23~0.49 V,能量效率提升范围为1.88%~16.06%。
  • 浙江省基础公益研究计划(LGG22E070003)
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2025年第55卷第4期
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doi: 10.19457/j.1001-2095.dqcd25719
  • 接收时间:2024-03-24
  • 首发时间:2025-10-30
  • 出版时间:2025-04-20
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  • 收稿日期:2024-03-24
  • 修回日期:2024-04-22
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浙江省基础公益研究计划(LGG22E070003)
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    1 中国计量大学 机电工程学院,浙江 杭州 310018
    2 华能国际电力江苏能源开发有限公司 清洁能源分公司,江苏 南京 210015
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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