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1、Newly progress of the Zn/Ni,single flow battery,Outline,IntroductionBackground,Newly progress,Experimental,Results of our teamResults of others,Conclusion,Acknowledgment,IntroductionIts urgent in demands of energy storage for use ofrenewable energies.frequency control,load regulation,UPS, andbackup
2、power sources,stabilizing electricity network and penetratingrenewable energy,IntroductionRedox flow battery, The,redox couples must be carried by the pumped,solutions; well-suited for transmission and distribution deferralapplications; The advantages: moderate cost, modularity,transportability and
3、flexible operation.+ Scheme of typical redoxflow cell: reversibleelectro-synthesis plant,Pump,Pump,2Br 2e, arge,2, 2e, arge,Zn , ,3,V 2,e, arg e,V , ,VO 2H e, arg e,IntroductionRedox flow battery, Those,RFB systems demonstrated at a large scale require,expensive materials; Aiming to reduce costs and
4、 simplify the cell design, somenew systems have been reported. But these systems stillhave shortcomings; A zinc nickel single flow battery is proposed by our team,in which almost no expensive materials are needed.,zinc/bromine flow battery,Br2Zn,chargedischchargedisch,ch arg edisch,all vanadium flow
5、 battery,2 disch,ch arg e,VO2 H2O, ,BackgroundZn/Ni single flow battery,2Ni(OH)2 2OH,2NiOOH2H2O2e,dischargecharge,Pos.,Zn4OH,Zn(OH)24 2e,dischargecharge,Neg.,+ _,Single electrolyte flow path, no membrane;,Modular, Scalable; Non-toxic; stable; Excellent Cycle life,NiOOHZn,泵,Zn(OH)42-aq.,tage(V) Volt,
6、ltage (V Vol,V),Capacity (mAh/cm ),BackgroundCoulombic efficiency of above 95% and energyefficiency of above 85% were obtained withlaboratory cell.,Fully charged,2,1.81.6,24h,2.01.51.0,positive (vs. Hg/HgO),5 C.E.70.6%,1.41.21.0,48h,0.50.0-0.5-1.0,Negative (vs. Hg/HgO),93.0%95.1%96.0%96.8%,0,5,10,15
7、,20,25,0,20,40,60,80 100 120,-1.5,2Self-discharge property (25mA/cm2),timeCharge/discharge curves (25mA/cm2),i / A Log,Io/Acm : 1.3310,1E-3,BackgroundZn/Ni single flow batteryZinc morphology, mossy and crystalline;Tafel ananalysis, i00.01A/cm2;0.10.01-1-1,:0.55-2 -2-1.40 -1.38 -1.36 -1.34 -1.32Poten
8、tial/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,0.050.040.030.020.01,-4 ,45,2+1 1: 06,Substrate0.0000.0020.004,CdPbCu,-1.6,-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.
9、4,0.0060.008,E (V vs. Hg/HgO),Scale up,Potential / Vvs. HgO/Hg,7.35Ah(100%DOD)77cm2,1.6,2.01.8,6A,3A 1.5A,10080,60,10080,Efficiency: Coulomb6A 91.6%3A 95.1%1.5 96.9%,Energy75.4%79.7%87.6%,604020,4020,80%DOD,0,2000,4000,6000,1.41.21.0,Capacity (mAh),0,cycle,02500 5000 7500 10000 12500,Experimental,Ne
10、wly 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 Shanpumps Co., ltd.Laboratory cell and scaled-up cell were usedto demonstrate the performance of the Zn/Nisingle flow battery.Laboratory cell, electrode a
11、rea: 7.0 cm7.0 cm;,Experimental,Newly progress,Electrochemical performance of singleelctrode was carried out using aSolartron 1280Z workstation with cyclicvoltammetry in a three-electrode,WE,configuration assembly consisting ofsintered nickel oxide as the counterelectrode, depsiting zinc as the work
12、ing,RE,CE,electrode and Hg/HgO as the referenceelectrode.working electrode: 2.0 cm2.0 cm;7.0 cm7.0 cm,Experimental,Newly progress,The charge and discharge characteristics of thecell were studied by applying a dc constant currentusing a Neware BTS 3000 battery test system(5V2000mA and 5V200A).,Labora
13、tory 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/LKOH + 0.5 mol/L LiOH;,The cell was charged up to 20 mAh/cm2 at thecurrent density of 5mA/cm2, 10mA/cm2;,2) ensity (A/cm Current de,m,) e Charge(C/cm Ac
14、cumulative,Charge(C/cm ) Accumulative,C,2,2,0,Results of our team,Newly progress,Cu foil,Iron mesh,Substrate,Ni foil,The mode of masstransportation ofIron mesh ischanged due tothe structure.,Iron mesh1 mV/s,0,2000,6000,8000,0-40-80,-1200-4-8,400010 mV/s,Ni foil1mV/s,0,6000,8000,0-100-200,0-10-20,200
15、0 400010 mV/s,-0.10-0.15,0.00 Cufoil-0.05,FemeshcoatedNi,20010050,600300200,800400250,1000500300,-1200-1-2-3-4-50 0-1-2-30,40030 mV/s20050 mV/s100 150Time(s),0 0-2-4-60-2-40,200 400 600 800-0.20 Nifoil30 mV/s-0.25100 200 300 400-1.6 -1.2 -0.8 -0.450 mV/s50 100 150 200 250 Potential(Vvs.Hg/HgO)Time(s
16、)程杰,文越华, 徐艳，物理化学学报, 已投稿,Chemical journal of Chinese universities, 2019, 32:1-4,I (cps),cps) I (c,-30mA/cm 40min,2-40mA/cm 30min,1- 60mA/cm 20min,- 80mA/cm 15min,Results of our team,Newly progress,Electrodeposition of preferentially oriented zinc,101,2,2,104,201,112,103110,102,100,002,2,5mA/cm2,20mA/
17、cm2,30mA/cm2,40mA/cm2,60mA/cm2,80mA/cm2,The effect of current on morphologyand crystal Structure of zinc,30,40,50,60,70,80,90,100,1,4h,3h,40min,30min,30min,30min,002,22.75,22.05,20.036,19.3,26.62,1.46,2,2,112,2(deg)103,100101102103,8.7341.396.056.03,8.9536.287.239.22,11.8136.376.337.61,9.7741.646.93
18、6.83,8.0431.636.899.86,1.18.1719.5436.5,101,110,102,1,110004,4.351.64,4.821.11,5.31.79,5.831.41,4.481.42,5.380,112,4.38,5.86,4.28,4.88,5.24,24.39,30,40,50,60,70,80,90,100,110,100,002,2 (deg),104,2,200201,1.143.5,03.5,1.372.22,03.34,0.772.85,00,104,0,0.94,1.71,0,1.4,3.42,g/HgO tial / V vs. Hg Potent,
19、acity /mA Cap,Ah,Results of our teamSintered Nickel electrode,0.80.6,Newly progressAfter 100cyclesAfter 300cyclesAfter 500cycles,Cycling,Discharge capacity /mAh (100&DOD, 8mol/LKOH),0.4,number 0.3M ZnO5 100100 100,0.4M ZnO10099.31,0.5M ZnO 0.6M ZnO 0.7M ZnO100 100 10098.19 97.75 98.02,200,99.23,98.5
20、2,98.91,98.72,96.83,0,5,10 15 20,25,0.20.0,0.6M ZnO,300,100,100,99.44,99.67,99.34,400,99.24,99.17,99.22,99.17,99.32,Capacity / mAh cm,-2,100,500 95.67 96.07 98.45 96.40 99.88The presence of zinc in KOHelectrolytes improves the cyclingstability of sintered nickel electrodes.,8060,no zinc80% DOD85% DO
21、D90% DOD95% DOD100% DOD,0 100 200 300 400 500 600cycleJie Cheng, Yuehua Wen, Gaoping Cao et. al. J. Power Sources, 196:1589, 2019,/% Efficiency Energy,E,/,fficiency /% Energy Ef,cy /% ergy Efficienc Ene,ciency /% Energy Effic,ciency /% Energy Effic,Efficiency /% Energy,E,%,i =15mAcm,20mAh/cm,25mAh/c
22、m,30mAh/cm,20mAh/cm,25mAh/cm,30mAh/cm,i = 25mA cm,20mAh/cm,25mAh/cm,30mAh/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 cyclingEffect of current and flow speed on the performance of Zn-Ni singleflow batteries and zinc de
23、position morphology were investigated.,70,9080,-2,70,9080,i = 15 mA cm,-2,70,9080,-2,0,20,6050403020100,222,0,20,6050403020100,222,0,20,6050 i = 15mA cm403020100,20mAh/cm25mAh/cm30mAh/cm,222,8070,90,8070,90,5 10 15CycleNumber,9080,5 10 15Cycle Number,5 10 15Cycle Number,6050403020100,6050403020100,2
24、22,-2,-220mAh/cm225mAh/cm230mAh/cm20 5 10 15 20,0,i = 25mA cm-25 10,15 20,0,15,20,706050403020100,222,5 10Cycle Number,Cycle Number Cycle NumberChemical journal of Chinese universities, 2019, 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 tem
25、peratureEnergy 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,1.81.6,1.81.6,E.E.2.1V 84.12%,1.81.6,E.E.2.1V 83.72%,0,1,2,3,1.41.2,Capacity(Ah),E.E.2.10V 79.60%2.15V 80.05%,0,1,2,3,4,1.41.2,Ca
26、pacity(Ah),0,1,2,3,4,1.41.2,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 efficiencyis 83.3% at current of 50A when the temperature isabout -20C.2.2,o
27、,1.8,o,o,1.8,2.0,2.1V,2.0V,oo,E.E.,0,50,100,150,1.61.41.2,Capacity(Ah),0,50,100,150,1.61.41.2,Capacity(Ah),E.E.2.0V 83.3%2.1V 82.4%,Charge/discharge at 50A(200Ah battery),Newly progress,Results of our teamScale up the cell,1.6V200Ah,oltage (V V,V),V,(V) Voltage,(,Cefficiency=95.2%,Cefficiency=97 5%,
28、Newly progress,Results of our team200Ah Zn/Ni single flow battery We settled on the 1.6V200Ah cell design.,Electrolyte velocity between electrode, 0.5 cm/s.2.01.8,1.0,1.61.41.2,Current=50.0A95 2%Eefficiency=80.8%,2.01.81.6,0,200,50 100 150Capacity (Ah),1.41.21.0,Current=100.0A=97.5%Eefficiency=75.9%
29、,0,50,100,150,200,Capacity (Ah),Newly progress,Results of our team200Ah Zn/Ni single flow battery Performance of the battery,age (V) Volta,Results of our team,Newly progress,200Ah Zn/Ni single flow battery50kWh energy storage system with 168 units of 200Ah Zn/Nisingle flow redox battery,Charge/disch
30、arge Limitsconditions18kW/18k 1.2VUc2.1VW 200U360V200A/200 1.2VUc2.1VA 200U370V,Charge Dischargeenergy energy68.30 kWh 55.21 kWh40.80 kWh 30.70 kWh,Energyefficiency80.8%75.2%,200,360340320300280260240220,Constant Power (18kW)Capacity(kWh),0,20,40,60,Newly progress,Results of our team300Ah Zn/Ni sing
31、le flow battery,Results of our team,Newly progress,300Ah Zn/Ni single flow battery Production line with a total capacity of up to 1megawatthours per year was designed and builded.,Results of others,Newly progress,Electrodeposition of preferentially oriented zincMossy50 C/cm2,Compactdendritic,Plot of
32、 arealfraction ofcompact zincversus the currentdensity ratioJournal of Power Sources 256 (2019) 145-152,Results of others,Newly progress,Gas evolution Oxygen evolution occurs during later period of thecharging process. Hydrogen is evolved throughout the cycling. The zinc electrode typically is more
33、Coulombicallyefficient than the nickel oxide electrode.H2,Journal of Power Sources 196 (2019) 6583-6587,Results of others,Newly progress,Improve power density by cell configuration Anovel cell structure is designed to reduce thepolarization of the positive electrode. The energy efficiency is improve
34、d 10.3% reaching to75.2% at 80 mA/cm2.,Journal of Power Sources 241 (2019) 196-202,Flow,Additional flow,Results of others,Newly progress,Effect of temperature The temperature sensitivity of CE and EE are 0.65%/Cand 0.98%/C.,The positive polarization is a major obstacle to enhancethe VE.,80 mA/cm2,Jo
35、urnal of Power Sources 249 (2019) 435-439,Results of othersenergy.cuny.edu/,Newly progress36kWh示范,Newly progress,Results of others555Ah Zn/Ni single flow battery,Journal of Power Sources 264 (2019) 49-58,Newly progress,Results of others555Ah Zn/Ni single flow battery,95th cycle,Journal of Power Sour
36、ces 264 (2019) 49-58,Conclusion,Iron mesh is suitable for the deposition of zinc.There exists electrodeposition of preferentially oriented,zinc, mainly influenced by current, zinc concentrationand flow flux. The presence of zinc in KOH electrolytes inhibitschanges in the cycling process as compared
37、to KOHelectrolytes with no zinc. The zinc deposition surface capacity is the mostimportant factor for the battery. The electrolyte flowspeed and current density must be settled to fit the crystalstructure of the zinc.,Conclusion,Oxygen evolution occurs during later period of thecharging process, and
38、 Hydrogen is evolved throughoutthe cycling.Power density of the battery can be improved by usinga special cell configuration.The battery can be used at low temperature. When thecurrent is higher (80 mA/cm2), the energy effeciencydecreases more quickly as the temperature gongingdown.Scale-up battery can give similar performance as labcell, and the demonstration system with capacity ofabove 50kWh goes well.,Acknowledgment,This work was supported by the National HighTechnology Research and Development Program (863Program, 2019AA052019) of China.,Thank you!,谢谢你的阅读,知识就是财富丰富你的人生,
