鎳鋅電池技術發(fā)展的最新研究總結.ppt

1、Newly progress of the Zn/Ni,single flow battery,Outline,Introduction Background,Newly progress,Experimental,Results of our team Results of others,Conclusion,Acknowledgment,Introduction Its urgent in demands of energy storage for use of renewable energies. frequency control,load regulation,UPS, and b

2、ackup power sources,stabilizing electricity network and penetrating renewable energy,Introduction Redox flow battery, The,redox couples must be carried by the pumped,solutions; well-suited for transmission and distribution deferral applications; The advantages: moderate cost, modularity, transportab

3、ility and flexible operation. + Scheme of typical redox flow cell: reversible electro-synthesis plant,Pump,Pump,2Br 2e, arge,2, 2e, arge,Zn , ,3,V 2,e, arg e,V , ,VO 2H e, arg e,Introduction Redox flow battery, Those,RFB systems demonstrated at a large scale require,expensive materials; Aiming to re

4、duce costs and simplify the cell design, some new systems have been reported. But these systems still have shortcomings; A zinc nickel single flow battery is proposed by our team, in which almost no expensive materials are needed.,zinc/bromine flow battery,Br2 Zn,charge disch charge disch,ch arg e d

5、isch,all vanadium flow battery,2 disch,ch arg e,VO2 H2O, ,Background Zn/Ni single flow battery,2Ni(OH)2 2OH,2NiOOH2H2O2e,discharge charge,Pos.,Zn4OH,Zn(OH)24 2e,discharge charge,Neg.,+ _,Single electrolyte flow path, no membrane;,Modular, Scalable; Non-toxic; stable; Excellent Cycle life,NiOOH Zn,泵,

6、Zn(OH)42- aq.,tage(V) Volt,ltage (V Vol,V),Capacity (mAh/cm ),Background Coulombic efficiency of above 95% and energy efficiency of above 85% were obtained with laboratory cell.,Fully charged,2,1.8 1.6,24h,2.0 1.5 1.0,positive (vs. Hg/HgO),5 C.E. 70.6%,1.4 1.2 1.0,48h,0.5 0.0 -0.5 -1.0,Negative (vs.

7、 Hg/HgO),93.0% 95.1% 96.0% 96.8%,0,5,10,15,20,25,0,20,40,60,80 100 120,-1.5,2 Self-discharge property (25mA/cm2),time Charge/discharge curves (25mA/cm2),i / A Log,Io/Acm : 1.3310,1E-3,Background Zn/Ni single flow battery Zinc morphology, mossy and crystalline; Tafel ananalysis, i00.01A/cm2; 0.1 0.01

8、 -1 -1,:0.55 -2 -2 -1.40 -1.38 -1.36 -1.34 -1.32 Potential/Vvs.Hg/HgO,Current / A,I (mA),ge (V) Voltag,tion(%) apacity retent Ca,Coulomb bic Efficiency y,CPb,/ M:,4: 5,2: 5 5:,6: 5,3: 10,Background, ,2,3,Additive,0.05 0.04 0.03 0.02 0.01,-4 ,4 5,2+ 1 1: 0 6,Substrate 0.000 0.002 0.004,Cd Pb Cu,-1.6,

9、-1.4 -1.2 -1.0 -0.8,-0.6,-0.03,0.00 -0.01 -0.02,1,-1.6,-1.2,-0.8,-0.4,0.006 0.008,E (V vs. Hg/HgO),Scale up,Potential / Vvs. HgO/Hg,7.35Ah(100%DOD) 77cm2,1.6,2.0 1.8,6A,3A 1.5A,100 80,60,100 80,Efficiency: Coulomb 6A 91.6% 3A 95.1% 1.5 96.9%,Energy 75.4% 79.7% 87.6%,60 40 20,40 20,80%DOD,0,2000,4000

10、,6000,1.4 1.2 1.0,Capacity (mAh),0,cycle,0 2500 5000 7500 10000 12500,Experimental,Newly progress,All,the chemicals of analytical grade purity,were used. The solvent of the solutions is distilled water. The pumps were made by Xin Xi Shan pumps Co., ltd. Laboratory cell and scaled-up cell were used t

11、o demonstrate the performance of the Zn/Ni single flow battery. Laboratory cell, electrode area: 7.0 cm7.0 cm;,Experimental,Newly progress,Electrochemical performance of single elctrode was carried out using a Solartron 1280Z workstation with cyclic voltammetry in a three-electrode,WE,configuration

12、assembly consisting of sintered nickel oxide as the counter electrode, depsiting zinc as the working,RE,CE,electrode and Hg/HgO as the reference electrode. working electrode: 2.0 cm2.0 cm; 7.0 cm7.0 cm,Experimental,Newly progress,The charge and discharge characteristics of the cell were studied by a

13、pplying a dc constant current using a Neware BTS 3000 battery test system (5V2000mA and 5V200A).,Laboratory cell,1.6V200Ah,Experimental,Newly progress,Solutions for CVs, different ZnO in different,KOH; Solutions for the cell, 1.0 mol/L ZnO + 10.0 mol/L KOH + 0.5 mol/L LiOH;,The cell was charged up t

14、o 20 mAh/cm2 at the current density of 5mA/cm2, 10mA/cm2;,2) ensity (A/cm Current de,m,) e Charge(C/cm Accumulative,Charge(C/cm ) Accumulative,C,2,2,0,Results of our team,Newly progress,Cu foil,Iron mesh,Substrate,Ni foil,The mode of mass transportation of Iron mesh is changed due to the structure.,

15、Iron mesh 1 mV/s,0,2000,6000,8000,0 -40 -80,-120 0 -4 -8,4000 10 mV/s,Ni foil 1mV/s,0,6000,8000,0 -100 -200,0 -10 -20,2000 4000 10 mV/s,-0.10 -0.15,0.00 Cufoil -0.05,FemeshcoatedNi,200 100 50,600 300 200,800 400 250,1000 500 300,-12 0 0 -1 -2 -3 -4 -5 0 0 -1 -2 -3 0,400 30 mV/s 200 50 mV/s 100 150 T

16、ime(s),0 0 -2 -4 -6 0 -2 -4 0,200 400 600 800 -0.20 Nifoil 30 mV/s -0.25 100 200 300 400 -1.6 -1.2 -0.8 -0.4 50 mV/s 50 100 150 200 250 Potential(Vvs.Hg/HgO) Time(s) 程杰,文越華, 徐艷，物理化學學報, 已投稿,Chemical journal of Chinese universities, 2011, 32:1-4,I (cps),cps) I (c,-30mA/cm 40min,2-40mA/cm 30min,1- 60mA

17、/cm 20min,- 80mA/cm 15min,Results of our team,Newly progress,Electrodeposition of preferentially oriented zinc,101,2,2,104,201,112,103 110,102,100,002,2,5mA/cm2,20mA/cm2,30mA/cm2,40mA/cm2,60mA/cm2,80mA/cm2,The effect of current on morphology and crystal Structure of zinc,30,40,50,60,70,80,90,100,1,4

18、h,3h,40min,30min,30min,30min,002,22.75,22.05,20.036,19.3,26.62,1.46,2,2,112,2(deg) 103,100 101 102 103,8.73 41.39 6.05 6.03,8.95 36.28 7.23 9.22,11.81 36.37 6.33 7.61,9.77 41.64 6.93 6.83,8.04 31.63 6.89 9.86,1.1 8.17 19.54 36.5,101,110,102,1,110 004,4.35 1.64,4.82 1.11,5.3 1.79,5.83 1.41,4.48 1.42,

19、5.38 0,112,4.38,5.86,4.28,4.88,5.24,24.39,30,40,50,60,70,80,90,100,110,100,002,2 (deg),104,2,200 201,1.14 3.5,0 3.5,1.37 2.22,0 3.34,0.77 2.85,0 0,104,0,0.94,1.71,0,1.4,3.42,g/HgO tial / V vs. Hg Potent,acity /mA Cap,Ah,Results of our team Sintered Nickel electrode,0.8 0.6,Newly progress After 100cy

20、cles After 300cycles After 500cycles,Cycling,Discharge capacity /mAh (100&DOD, 8mol/LKOH),0.4,number 0.3M ZnO 5 100 100 100,0.4M ZnO 100 99.31,0.5M ZnO 0.6M ZnO 0.7M ZnO 100 100 100 98.19 97.75 98.02,200,99.23,98.52,98.91,98.72,96.83,0,5,10 15 20,25,0.2 0.0,0.6M ZnO,300,100,100,99.44,99.67,99.34,400

21、,99.24,99.17,99.22,99.17,99.32,Capacity / mAh cm,-2,100,500 95.67 96.07 98.45 96.40 99.88 The presence of zinc in KOH electrolytes improves the cycling stability of sintered nickel electrodes.,80 60,no zinc 80% DOD 85% DOD 90% DOD 95% DOD 100% DOD,0 100 200 300 400 500 600 cycle Jie Cheng, Yuehua We

22、n, Gaoping Cao et. al. J. Power Sources, 196:1589, 2011,/% Efficiency Energy,E,/,fficiency /% Energy Ef,cy /% ergy Efficienc Ene,ciency /% Energy Effic,ciency /% Energy Effic,Efficiency /% Energy,E,%,i =15mAcm,20mAh/cm,25mAh/cm,30mAh/cm,20mAh/cm,25mAh/cm,30mAh/cm,i = 25mA cm,20mAh/cm,25mAh/cm,30mAh/

23、cm,20mAh/cm,25mAh/cm,30mAh/cm,i = 25mA cm,Results of our team,Newly progress,5.75 L/ min,3.45 L/ min,5.25 L/ min,Stability of cycling Effect of current and flow speed on the performance of Zn-Ni single flow batteries and zinc deposition morphology were investigated.,70,90 80,-2,70,90 80,i = 15 mA cm

24、,-2,70,90 80,-2,0,20,60 50 40 30 20 10 0,2 2 2,0,20,60 50 40 30 20 10 0,2 2 2,0,20,60 50 i = 15mA cm 40 30 20 10 0,20mAh/cm 25mAh/cm 30mAh/cm,2 2 2,80 70,90,80 70,90,5 10 15 CycleNumber,90 80,5 10 15 Cycle Number,5 10 15 Cycle Number,60 50 40 30 20 10 0,60 50 40 30 20 10 0,2 2 2,-2,-2 20mAh/cm2 25mA

25、h/cm2 30mAh/cm2 0 5 10 15 20,0,i = 25mA cm-2 5 10,15 20,0,15,20,70 60 50 40 30 20 10 0,2 2 2,5 10 Cycle Number,Cycle Number Cycle Number Chemical journal of Chinese universities, 2011, 32:1-4,Voltage(V,V),Voltage(V,V),Voltage(V,V),40 C,0C,-20 C,Results of our team,Newly progress,Effect of temperatur

26、e Energy efficiency is almost stable as temperature decreases. (Results of 3.6Ah battery.),*(Rate: 0.55C, Charge: Capacity 3.95Ah/2.1V),2.0,2.2,o,2.0,2.2,o,2.0,2.2,o,1.8 1.6,1.8 1.6,E.E. 2.1V 84.12%,1.8 1.6,E.E. 2.1V 83.72%,0,1,2,3,1.4 1.2,Capacity(Ah),E.E. 2.10V 79.60% 2.15V 80.05%,0,1,2,3,4,1.4 1.

27、2,Capacity(Ah),0,1,2,3,4,1.4 1.2,Capacity(Ah),tage(V) Volt,age(V) Volta,-20 C,20,-30C,-20 C,VHigh,-20 C 82.4%,-30 C 79.4%,Results of our team,Newly progress,2.0,Effect of temperature Results of 200Ah battery show that the energy efficiency is 83.3% at current of 50A when the temperature is about -20

28、C. 2.2,o,1.8,o,o,1.8,2.0,2.1V,2.0V,o o,E.E.,0,50,100,150,1.6 1.4 1.2,Capacity(Ah),0,50,100,150,1.6 1.4 1.2,Capacity(Ah),E.E. 2.0V 83.3% 2.1V 82.4%,Charge/discharge at 50A(200Ah battery),Newly progress,Results of our team Scale up the cell,1.6V200Ah,oltage (V V,V),V,(V) Voltage,(,Cefficiency=95.2%,Ce

29、fficiency=97 5%,Newly progress,Results of our team 200Ah Zn/Ni single flow battery We settled on the 1.6V200Ah cell design.,Electrolyte velocity between electrode, 0.5 cm/s. 2.0 1.8,1.0,1.6 1.4 1.2,Current=50.0A 95 2% Eefficiency=80.8%,2.0 1.8 1.6,0,200,50 100 150 Capacity (Ah),1.4 1.2 1.0,Current=1

30、00.0A =97.5% Eefficiency=75.9%,0,50,100,150,200,Capacity (Ah),Newly progress,Results of our team 200Ah Zn/Ni single flow battery Performance of the battery,age (V) Volta,Results of our team,Newly progress,200Ah Zn/Ni single flow battery 50kWh energy storage system with 168 units of 200Ah Zn/Ni singl

31、e flow redox battery,Charge/ discharge Limits conditions 18kW/18k 1.2VUc2.1V W 200U360V 200A/200 1.2VUc2.1V A 200U370V,Charge Discharge energy energy 68.30 kWh 55.21 kWh 40.80 kWh 30.70 kWh,Energy efficiency 80.8% 75.2%,200,360 340 320 300 280 260 240 220,Constant Power (18kW) Capacity(kWh),0,20,40,

32、60,Newly progress,Results of our team 300Ah Zn/Ni single flow battery,Results of our team,Newly progress,300Ah Zn/Ni single flow battery Production line with a total capacity of up to 1 megawatthours per year was designed and builded.,Results of others,Newly progress,Electrodeposition of preferentia

33、lly oriented zinc Mossy 50 C/cm2,Compact dendritic,Plot of areal fraction of compact zinc versus the current density ratio Journal of Power Sources 256 (2014) 145-152,Results of others,Newly progress,Gas evolution Oxygen evolution occurs during later period of the charging process. Hydrogen is evolv

34、ed throughout the cycling. The zinc electrode typically is more Coulombically efficient than the nickel oxide electrode. H2,Journal of Power Sources 196 (2011) 6583-6587,Results of others,Newly progress,Improve power density by cell configuration Anovel cell structure is designed to reduce the polar

35、ization of the positive electrode. The energy efficiency is improved 10.3% reaching to 75.2% at 80 mA/cm2.,Journal of Power Sources 241 (2013) 196-202,Flow,Additional flow,Results of others,Newly progress,Effect of temperature The temperature sensitivity of CE and EE are 0.65%/C and 0.98%/C.,The pos

36、itive polarization is a major obstacle to enhance the VE.,80 mA/cm2,Journal of Power Sources 249 (2014) 435-439,Results of others /,Newly progress 36kWh示范,Newly progress,Results of others 555Ah Zn/Ni single flow battery,Journal of Power Sources 264 (2014) 49-58,Newly progress,Results of others 555Ah Zn/Ni single flow battery,95th cycle