阀控式密封铅酸电池脉冲充电机理及其实现的研究
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摘要
本文综述了阀控式密封铅酸(VRLA)电池的发展历史、充电模式的现状及其引起的失效模式，在研究了VRLA电池的充电特点和脉冲充电的机理和优势的基础上提出了脉冲充电技术．
运用开关电源技术和单片机控制等技术设计和制作了智能脉冲充电器，实现了正负交替的脉冲充电，所得的脉冲充电波形满足了要求．通过程序实现了对脉冲充电参数的可调设置，满足了脉冲充电的参数探索的要求。
在部分荷电状态(PSOC)下采用不同的充电模式，对电动车(EV)电池进行了100％放电深度(DOD)的对比试验，对混和电动车(HEV)电池在高倍率部分荷电状态(HRPSOC)下的循环进行了实验。发现在脉冲充电模式下的循环寿命具有明显优势。对上述实验中失效的电池进行了脉冲充电容量恢复实验。发现脉冲充电具有很好的容量恢复作用。对所得的结果运用正负极电位、SEM、XRD等物理测试手段进行了分析。研究表明，脉冲充电提高了活性物质与界面的电导及机械强度，抑制形成和激活非活性的硫酸铅，从而有效地提高了电池的循环寿命。
本文对不同的脉冲充电参数进行了实验和研究，提出适应不同电池和不同领域中VRLA电池的脉冲充电方法和参数，找到了一条在实际应用中避免或缓解电池失效的有效途径。
The development history and the present status of charging algorithms and the failure modes caused by it for valve-regulated lead-acid (VRLA) batteries are reviewed in this paper.Based on the studies on the charge features and the pulse charging principle of VRLA batteries a novel pulse charging technique is presented in this paper.
A novel intelligence charging device is designed and made using technique of on-off power source and micro-control, which can generate positive/negative pulse charging and the result of pulse charging curver verify the proposed scheme. The parameters of pulse charging can be seted using program and meet the experimental require of researching pulse charging's the parameters.
Under the partial state of charge (PSOC), the 100% Deepth of Discharge (DOD) experiments for the EV battery were made by using different charging algorithms.Under the high rate partial state of charge (HRPSOC) , the re-cycle experiments for the HEV battery were made. Also the recover experiments for the failed battery on the above experiments were made by using pulse charging algorithms. The experiments indicate that pulse-charge algorithm can make battery a good cycle life and pulse- charge has a good recovery effect on failed EV battery and failed HEV battery. The experimental results from different algorithms were analyzed by the positive and negative voltage testing method, SEM,XRD measurements etc. This research works show that the electric conductivity and the mechanical strength of both the active material and the interface are much improved, and the generation of the non-active Pbso_4 can be effectivily suppressed and its reactivation is effectively improved so that the re-cycle life of VRLA battery is greatly improved by using this method.
The experiments and research of different pulse charging parameters were made in this paper. The pulse charging algorithms and its parameters that adapt different VRLA battery in different fields is presented. One good way that slove or slow battery's fail in the fact use was found.
运用开关电源技术和单片机控制等技术设计和制作了智能脉冲充电器，实现了正负交替的脉冲充电，所得的脉冲充电波形满足了要求．通过程序实现了对脉冲充电参数的可调设置，满足了脉冲充电的参数探索的要求。
在部分荷电状态(PSOC)下采用不同的充电模式，对电动车(EV)电池进行了100％放电深度(DOD)的对比试验，对混和电动车(HEV)电池在高倍率部分荷电状态(HRPSOC)下的循环进行了实验。发现在脉冲充电模式下的循环寿命具有明显优势。对上述实验中失效的电池进行了脉冲充电容量恢复实验。发现脉冲充电具有很好的容量恢复作用。对所得的结果运用正负极电位、SEM、XRD等物理测试手段进行了分析。研究表明，脉冲充电提高了活性物质与界面的电导及机械强度，抑制形成和激活非活性的硫酸铅，从而有效地提高了电池的循环寿命。
本文对不同的脉冲充电参数进行了实验和研究，提出适应不同电池和不同领域中VRLA电池的脉冲充电方法和参数，找到了一条在实际应用中避免或缓解电池失效的有效途径。
The development history and the present status of charging algorithms and the failure modes caused by it for valve-regulated lead-acid (VRLA) batteries are reviewed in this paper.Based on the studies on the charge features and the pulse charging principle of VRLA batteries a novel pulse charging technique is presented in this paper.
A novel intelligence charging device is designed and made using technique of on-off power source and micro-control, which can generate positive/negative pulse charging and the result of pulse charging curver verify the proposed scheme. The parameters of pulse charging can be seted using program and meet the experimental require of researching pulse charging's the parameters.
Under the partial state of charge (PSOC), the 100% Deepth of Discharge (DOD) experiments for the EV battery were made by using different charging algorithms.Under the high rate partial state of charge (HRPSOC) , the re-cycle experiments for the HEV battery were made. Also the recover experiments for the failed battery on the above experiments were made by using pulse charging algorithms. The experiments indicate that pulse-charge algorithm can make battery a good cycle life and pulse- charge has a good recovery effect on failed EV battery and failed HEV battery. The experimental results from different algorithms were analyzed by the positive and negative voltage testing method, SEM,XRD measurements etc. This research works show that the electric conductivity and the mechanical strength of both the active material and the interface are much improved, and the generation of the non-active Pbso_4 can be effectivily suppressed and its reactivation is effectively improved so that the re-cycle life of VRLA battery is greatly improved by using this method.
The experiments and research of different pulse charging parameters were made in this paper. The pulse charging algorithms and its parameters that adapt different VRLA battery in different fields is presented. One good way that slove or slow battery's fail in the fact use was found.
引文
1 宋文顺．化学电源工艺学(M)．中国轻工业出版社．1995：104-105
2 胡信国，王金玉．阀控式密封铅酸蓄电池地发展．电源技术．1998，(6)：265-269
3 R.H.Newnham. Advantages and disadvantages of valve-regulated lead/acid batteries. J. Power Sources. 1994, 52:149-153
4 K.Suzuki, K.Nisida. Valve-Regulated Lead/Acid Batteries for Electric-Vehicle. J. Power Sources. 1996,59:167-175
5 忻元敏．电动自行车发展现状和展望．浙江自行车．1997，4：14-23
6 K. Peter. Automotive battery energy density -past, present and future. J. Power Sources. 1991,33:247-255
7 E T. Moseley, Characteristics of a high-performance lead/acid battery for electric vehicles-an ALABC view. J. Power Sources. 1997,67:115-119
8 Ttistan Juergens, Robert.F,.Nelson. A new high-rate, fast-charge lead/acid battery. J. Power Sourecs.
9 周明明，周龙瑞，方建军．电动自行车用小密铅蓄电池的研制．浙江自行车，19973：18-28
10 游兆高．电动车铅蓄电池特性及发展趋势．电池．1995，25(4)：184-185
11 宋丰章．电动车用铅酸蓄电池．电池。1996，26(3)：126-127
12 胡信国，童一波．阀控式密封铅酸蓄电池的最新发展．蓄电池．2001，(3)：
13 M.D.Anda, Are valve-regulated Lead-acid batteries reliable, An end-used perspective, International Lead Zinc Research Organzation(ILZRO), Sandia National Laboratories, Advanced Lead-acid battery Consortium(ALABC)
14 D.A.J.Rand, ET.Moseley.valve-regulated lead-acid batteries. Elsevier B.V.2004,241-291
15 刘宗光，林涛可延长电动自行车电池寿命的充电模式(电池)2005，35(4)：285-287
16 L.T.Lam, N.P. Haigh, Novel technique to ensure battery reliability in 42-V PowerNets for new-generation automobiles (J).J.Power Source. 144 (2005) 552-559
17 Dimitrov. M, Pavlov .D. Influence of grid alloy and fast charge on battery cycle life and structure of the positive active mass of lead acid batteries. Power Sources, 2001:234—257
18 Yah Zhigong. Influence of the charging mode on the performances of lead/acid batteries used for electrical vehicles. Batteries, 2001(6) :261—163
19 包有富，深循环电池充电模式的研究．电池，2002(1)：30～31
20 L.T.Lam,H.Ozgun,Pulsed-current charging of lead/acid batteries-a possible means for overcoming premature capacity loss (J).J.Power Source 53 (1995)
21 Hsieh, Y.C.; Moo, C.S.; Wu, C.K.; Cheng, J.C. non-dissipative reflex charging circuit, Telecommunications Energy Conference, 2003. INTELEC '03. The 25th International, 19-23 Oct. 2003 Page(s):679-683
22 Huang-Jen Chiu; Ping-Lung Pan; Wei-Hao Yeh.A novel rapid charger of lead-acid batteries with energy recovery, Applied Power Electronics Conference and Exposition, 2003. APEC '03. Eighteenth Annual IEEE Volume 2, 9-13 Feb. 2003 Page(s):756-759 vol.2
23 杭瑚．铅酸蓄电池的早期容量损失．蓄电池．1994，(4)：2
24 R. David Prengaman,the impact of ALABC research results on battery design [J]. The battery Man, 2000, (9) : 16-25
25 孔德龙，阎新华等．提高阀控铅酸蓄电池充电接受能力的研究．蓄电池．2001，(6)：12-15
26 D.Pavlov. A Theory of the Grid/Positive Active Mass(PAM) Interface and Possible Methods to Improve PAM Utilization and Cycle Life of Lead/Acid Batteries. J. of Power Sources. 1995, (53) :9-21
27 W B.Brecht,Reactions in VRLA batteries, The Battery Man,1998, 40(5): 24-45
28 Winsel A, Voss E, Hullmeine U,The aggomerate of spheres (Kugelhaufem) mode of the the PbO2/PbSO4 electrode J. Power Sources, 1990;30(1-4):209-226
29 D.Pavlov, Premature capacity loss (PCL) of the positive lead acid battery plate; A new concept to describe the phenomenon. J. Power Sources, 1993,42(3):345-363
30 D.Pavlov, Suppression of premature capacity loss by methods based on the gel crystal concept of PbO_2 electrode.J.Power Sources, 1993,46(2-3):171-190
31 D.Pavlov, Influence of crystal and gel zones on the capacity of the lead dioxide active mass (extened abstract). J Power Sources, 1993,46(2-3):171-190
32 刘军贤，杨秀敏。阀控式密封铅酸蓄电池早期容量失效问题的分析与研究．电源技术．1997，(5)：70-73
33 L.Albert,A.Chabrol, L.Torcheux, Ph.Steyer.J.EHilger.Improved lead alloys for lead～acid positive grids in electric vehicle application J.Power Sources, 1997,67:257-265
34 E Ruetschi, Review on the lead-acid battery science and technology, J. Power Sources 2 (1977-1978) 3-24
35 Y. Yamaguchi, M. Shiota, Y. Hirai, S. Hara, Combined in situ EC-AFM and CV measurement study on lead electrode for lead-acid batteries, J. Power Sources 93 (2001) 104-111
36 A. Winsel, E. Voss, U. Hullmeine, The aggregate-of-spheres (Kugel-haufen) model of the PbO_2/PbSO_4 electrode, J. Power Sources 30 (1990) 209-226
37 U. Hullmeine, A. Winsel, E. Voss, Effect of previous charge/discharge history on the capacity of the PbO_2/PbSO_4 electrode:the hysteresis or memory effect, J. Power Sources 25(1989) 27-47
38 E. Meissner, E. Voss, Reversible capacity decay of positive electrodes in lead-acid cells, J. Power Sources 33 (1991) 231-244
39 D. Pavlov, G. Petkova, M. Dimitriv, M. Shimoni, M. Tsubota, Influence of fast-charge on the cycle life of positive lead-acid battery plates, J. Power Sources 87 (2000) 29-56
40 朱松然，蓄电池手册．天津大学出版社出版．1998年7月第1版
41 P. Ruetschi, Silver-silver sulfate reference electrodes for lead-acid batteries, J. Power Sources 116 (2003) 53-60
42 马以春，王坚．慢脉充快速充电方法析气性能研究．电源技术．2004．28(6)
43 纪化成，赵晓兰．阀控式铅酸蓄电池的热失控．蓄电池．1997，(1)：24-25
44 D.A.J.Rand, P.T.Moseley.valve-regulated lead-acid batteries. Elsevier B.V.2004,241-291
45 罗光毅，《蓄电池智能管理系统》，硕士论文，浙江大学，2003．3
46 潘尚智，VRLA蓄电池管理系统，硕士论文，浙江大学，2001．4
47 Pei-Hsuan Cheng A high-efficiency fast charger for lead-acid batteries; IECON 02 [Industrial Electronics Society, IEEE 2002 28th Annual Conference of the], 2002 On page(s): 1410-1415 vol.2
48 李江洪，一种新型电池脉冲充电机的设计．江南航天科技．1997，(3)：31-37
49 李学海，PIC单片机实用教程．北京航天航空大学出版社，2002．2
50 李荣正，PIC单片机原理及应用．北京航天航空大学出版社，2005年1月版，2005年1月第1次印刷
51 张占松 蔡宣三，开关电源的原理与设计，电子工业出版社，1998年7月版
52 薛永毅 王淑英，新型电源电路应用实例，电子工业出版社，2001年10月版，pp353—354
2 胡信国，王金玉．阀控式密封铅酸蓄电池地发展．电源技术．1998，(6)：265-269
3 R.H.Newnham. Advantages and disadvantages of valve-regulated lead/acid batteries. J. Power Sources. 1994, 52:149-153
4 K.Suzuki, K.Nisida. Valve-Regulated Lead/Acid Batteries for Electric-Vehicle. J. Power Sources. 1996,59:167-175
5 忻元敏．电动自行车发展现状和展望．浙江自行车．1997，4：14-23
6 K. Peter. Automotive battery energy density -past, present and future. J. Power Sources. 1991,33:247-255
7 E T. Moseley, Characteristics of a high-performance lead/acid battery for electric vehicles-an ALABC view. J. Power Sources. 1997,67:115-119
8 Ttistan Juergens, Robert.F,.Nelson. A new high-rate, fast-charge lead/acid battery. J. Power Sourecs.
9 周明明，周龙瑞，方建军．电动自行车用小密铅蓄电池的研制．浙江自行车，19973：18-28
10 游兆高．电动车铅蓄电池特性及发展趋势．电池．1995，25(4)：184-185
11 宋丰章．电动车用铅酸蓄电池．电池。1996，26(3)：126-127
12 胡信国，童一波．阀控式密封铅酸蓄电池的最新发展．蓄电池．2001，(3)：
13 M.D.Anda, Are valve-regulated Lead-acid batteries reliable, An end-used perspective, International Lead Zinc Research Organzation(ILZRO), Sandia National Laboratories, Advanced Lead-acid battery Consortium(ALABC)
14 D.A.J.Rand, ET.Moseley.valve-regulated lead-acid batteries. Elsevier B.V.2004,241-291
15 刘宗光，林涛可延长电动自行车电池寿命的充电模式(电池)2005，35(4)：285-287
16 L.T.Lam, N.P. Haigh, Novel technique to ensure battery reliability in 42-V PowerNets for new-generation automobiles (J).J.Power Source. 144 (2005) 552-559
17 Dimitrov. M, Pavlov .D. Influence of grid alloy and fast charge on battery cycle life and structure of the positive active mass of lead acid batteries. Power Sources, 2001:234—257
18 Yah Zhigong. Influence of the charging mode on the performances of lead/acid batteries used for electrical vehicles. Batteries, 2001(6) :261—163
19 包有富，深循环电池充电模式的研究．电池，2002(1)：30～31
20 L.T.Lam,H.Ozgun,Pulsed-current charging of lead/acid batteries-a possible means for overcoming premature capacity loss (J).J.Power Source 53 (1995)
21 Hsieh, Y.C.; Moo, C.S.; Wu, C.K.; Cheng, J.C. non-dissipative reflex charging circuit, Telecommunications Energy Conference, 2003. INTELEC '03. The 25th International, 19-23 Oct. 2003 Page(s):679-683
22 Huang-Jen Chiu; Ping-Lung Pan; Wei-Hao Yeh.A novel rapid charger of lead-acid batteries with energy recovery, Applied Power Electronics Conference and Exposition, 2003. APEC '03. Eighteenth Annual IEEE Volume 2, 9-13 Feb. 2003 Page(s):756-759 vol.2
23 杭瑚．铅酸蓄电池的早期容量损失．蓄电池．1994，(4)：2
24 R. David Prengaman,the impact of ALABC research results on battery design [J]. The battery Man, 2000, (9) : 16-25
25 孔德龙，阎新华等．提高阀控铅酸蓄电池充电接受能力的研究．蓄电池．2001，(6)：12-15
26 D.Pavlov. A Theory of the Grid/Positive Active Mass(PAM) Interface and Possible Methods to Improve PAM Utilization and Cycle Life of Lead/Acid Batteries. J. of Power Sources. 1995, (53) :9-21
27 W B.Brecht,Reactions in VRLA batteries, The Battery Man,1998, 40(5): 24-45
28 Winsel A, Voss E, Hullmeine U,The aggomerate of spheres (Kugelhaufem) mode of the the PbO2/PbSO4 electrode J. Power Sources, 1990;30(1-4):209-226
29 D.Pavlov, Premature capacity loss (PCL) of the positive lead acid battery plate; A new concept to describe the phenomenon. J. Power Sources, 1993,42(3):345-363
30 D.Pavlov, Suppression of premature capacity loss by methods based on the gel crystal concept of PbO_2 electrode.J.Power Sources, 1993,46(2-3):171-190
31 D.Pavlov, Influence of crystal and gel zones on the capacity of the lead dioxide active mass (extened abstract). J Power Sources, 1993,46(2-3):171-190
32 刘军贤，杨秀敏。阀控式密封铅酸蓄电池早期容量失效问题的分析与研究．电源技术．1997，(5)：70-73
33 L.Albert,A.Chabrol, L.Torcheux, Ph.Steyer.J.EHilger.Improved lead alloys for lead～acid positive grids in electric vehicle application J.Power Sources, 1997,67:257-265
34 E Ruetschi, Review on the lead-acid battery science and technology, J. Power Sources 2 (1977-1978) 3-24
35 Y. Yamaguchi, M. Shiota, Y. Hirai, S. Hara, Combined in situ EC-AFM and CV measurement study on lead electrode for lead-acid batteries, J. Power Sources 93 (2001) 104-111
36 A. Winsel, E. Voss, U. Hullmeine, The aggregate-of-spheres (Kugel-haufen) model of the PbO_2/PbSO_4 electrode, J. Power Sources 30 (1990) 209-226
37 U. Hullmeine, A. Winsel, E. Voss, Effect of previous charge/discharge history on the capacity of the PbO_2/PbSO_4 electrode:the hysteresis or memory effect, J. Power Sources 25(1989) 27-47
38 E. Meissner, E. Voss, Reversible capacity decay of positive electrodes in lead-acid cells, J. Power Sources 33 (1991) 231-244
39 D. Pavlov, G. Petkova, M. Dimitriv, M. Shimoni, M. Tsubota, Influence of fast-charge on the cycle life of positive lead-acid battery plates, J. Power Sources 87 (2000) 29-56
40 朱松然，蓄电池手册．天津大学出版社出版．1998年7月第1版
41 P. Ruetschi, Silver-silver sulfate reference electrodes for lead-acid batteries, J. Power Sources 116 (2003) 53-60
42 马以春，王坚．慢脉充快速充电方法析气性能研究．电源技术．2004．28(6)
43 纪化成，赵晓兰．阀控式铅酸蓄电池的热失控．蓄电池．1997，(1)：24-25
44 D.A.J.Rand, P.T.Moseley.valve-regulated lead-acid batteries. Elsevier B.V.2004,241-291
45 罗光毅，《蓄电池智能管理系统》，硕士论文，浙江大学，2003．3
46 潘尚智，VRLA蓄电池管理系统，硕士论文，浙江大学，2001．4
47 Pei-Hsuan Cheng A high-efficiency fast charger for lead-acid batteries; IECON 02 [Industrial Electronics Society, IEEE 2002 28th Annual Conference of the], 2002 On page(s): 1410-1415 vol.2
48 李江洪，一种新型电池脉冲充电机的设计．江南航天科技．1997，(3)：31-37
49 李学海，PIC单片机实用教程．北京航天航空大学出版社，2002．2
50 李荣正，PIC单片机原理及应用．北京航天航空大学出版社，2005年1月版，2005年1月第1次印刷
51 张占松 蔡宣三，开关电源的原理与设计，电子工业出版社，1998年7月版
52 薛永毅 王淑英，新型电源电路应用实例，电子工业出版社，2001年10月版，pp353—354