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1 能源科技與環境概論儲能電池導論 Hsing-Yu Tuan ( 段興宇 ) Department of Chemical Engineering, National Tsing- Hua University

2 How Electrochemical Batteries Work REDOX Reaction Electron Flow Anode Oxidation, the loss of electrons, occurs at the anode Salt Bridge Cathode Electrolyte Electrolyte Reduction, the gain of electrons, occurs at the cathode.

3 The Periodic Table: choose the electrode Combination of electrodes to make a variety types of batteries: lithium ion battery nickel-zinc zinc air Nickel cadmium Ni iron Silver zinc Mercury cell

4 The History of Battery Volta piles Baghdad battery Lithium ion battery -sony

Short battery life The Daniel Cell Invented in 1836 by John Daniell The lead-acid cell Invented

5 Electrochemical Battery History Cont d The Voltaic Pile Invented by Alessandro Volta in 1800 Zinc and Copper with a cloth soaked in brine Technical Flaws: Compressing of cloth created shorts Short battery life The Daniel Cell Invented in 1836 by John Daniell The lead-acid cell Invented in 1859 by Gaston Planté First rechargeable battery The zinc-carbon cell Invented in 1887 by Carl Gassner

6 Electrochemical Battery History Cont d The Nickel-Cadmium Battery Invented in 1899 by Waldmar Jungner. The common Alkaline Battery Invented in 1955 by Lewis Urry The Nickel Metal-Hydrid Battery NiMH batteries for smaller applications started to be on the market in Lithium and Lithium-ion Batteries First lithium batteries sold in the 1970s First lithium-ion batteries sold in 1991 portable electronic devices First lithium-ion polymer batteries released in 1996

7 伏特電池的原理在稀硫酸中插入銅板和鋅版兩種電極鋅金屬變成鋅離子溶出 Zn+2 鋅變成負電銅板不會融化, 但因電子被 H+ 帶走帶著一點正電以導線連接鋅版和銅板則會產生電流, 直到鋅版耗盡

8 Various kinds of batteries

9 Primary vs. Secondary Batteries Primary batteries are disposable:their electrochemical reaction cannot be reversed. Secondary batteries are rechargeable, because their electrochemical reaction can be reversed by applying a certain voltage to the battery in the opposite direction of the discharge.

10 可逆化學反應與不可逆化學反應

11 Terminology and Units Primary Batteries Disposable Secondary Batteries Rechargeable emf Electromotive force, voltage Ampere hour (Ah) = 3600 coulombs, a measure of electric charge Watt hour (Wh) = 3600 joules, a measure of energy Ah = (Wh) / emf

12 Theoretical Cell voltage Anode (oxidation potential)+ cathode (reduction potential)=standard cell potential Zn+Cl 2 ZnCl 2 Zn Zn +2 +2e -(-0.76 V) Cl 2 2Cl - -2e 1.36V E o = 2.12 V theoretical voltage

13 Theoretical capacity Zn + Cl2 ZnCl Ah/g 0.76 Ah/g 1.22g/Ah 1.32g/Ah = 2.54 gah or 0.394/Ah/g

14 Primary Alkaline Batteries Can lose 8 20% charge every year at room tempurature. Discharge performance drops at low temperatures. AAA AA 9V C D Capacity (Ah) Voltage Energy (Wh)

15 Secondary Alkaline Batteries Self-discharge more quickly than primary batteries Low-Capacity NiMH ( mah) High-Capacity NiMH (2500+ mah) NiCd Charge Cycles Must not overcharge because that will damage the batteries. Quick charges will also damage the batteries. Must not over-discharge. NiCd has memory effect. NiCd is better for applications where current draw is less than the battery s own self-discharge rate. NiMH have a higher capacity, are cheaper, and are less toxic than NiCd.

Source: wiki Recharge-ability & the memory effect Recharge-ability: basically, when the direction of electron discharge (negative to positive) is reversed, restoring power.

16 Source: wiki Recharge-ability & the memory effect Recharge-ability: basically, when the direction of electron discharge (negative to positive) is reversed, restoring power. the Memory Effect: - The battery appears to "remember" the smaller capacity - the term 'memory' came from an aerospace nickel-cadmium application in which the cells were repeatedly discharged to 25% of available capacity by exacting computer control, then recharged to 100% capacity without overcharge. This long-term, repetitive cycle regime, with no provision for overcharge, resulted in a loss of capacity beyond the 25% discharge point. Hence the birth of a "memory" phenomenon, whereby nickel-cadmium batteries purportedly lose capacity if repeatedly discharged to a specific level of capacity.

The electrodes are zinc and carbon, with an acidic paste between them serve as the

17 Types of Batteries Zinc-Carbon: used in all inexpensive AA, C, and D dry-cell batteries. The electrodes are zinc and carbon, with an acidic paste between them serve as the electrolyte (disposable) Alkaline: Curalcell or Energizer cell batteries. The electrodes are zinc and manganese-oxide, with an alkaline electrolyte (disposable)

18 Modern batteries Lead-Acid: used in cars: the electrodes are lead and lead-oxide, with an acidic electrolyte (rechargeable) Lithium-ion batteries - rechargeable and no memory effect Fuel cells

19 碳鋅電池電壓 :1.5V 正極 : 二氧化錳負極 : 鋅電解液 :NH4Cl ZnCl2

20 Battery Aspects Energy Density: total amount of energy that can be stored per unit mass or volume how long will your laptop run by a fully-charged cell. Power Density: Maximum rate of energy discharge per unit mas or volume. Low power: laptop, ipod high power car Safety: could sustain at high temperatures Life: stability of energy density and power density with repeated cycling is needed for the long life required in many applications. Cost: Must compete with other energy storage technologies

21 Lithium ion battery

22 Lithium Periodic Table Symbol: Li Atomic Weight: 3 (light!) Like sodium and potassium, an alkali metal. (Group 1 #s 1 through 7) Highly reactive, with a high energy density. Used to treat manic-depression because it is particularly effective at calming a person in a manic state. The most electropositive (-3.04V versus standard hydrogen electrode

23 鋰離子電池的結構正極活性物質 (LiCoO2\LiMnO2\LiNixCo1-xO2) 導電劑溶劑粘合劑基體負極活性物質 ( 石墨 MCMB) 粘合劑溶劑基體隔膜 (PP+PE) 電解液 (LiPF6 + DMC EC EMC) 外殼五金件 ( 鋁殼蓋板極耳絕緣片 )

24 Composition of Li-ion batteries

25 Lithium Ion Battery Development Pioneering work for the lithium battery bagan in 1912 by G. N. Lewis but it was not until the early 1970 s when the first non-rechargeable lithium batteries became commercially availble In the 1970 s Lithium metal was used but its instability rendered it unsafe

26 Why lithium-ion other than Lithium 鋰電池的負極採用金屬鋰, 在充電過程中金屬鋰會在鋰負極上沉積, 產生枝晶鋰, 造成電池內部短路產生爆炸鋰離子電池則採用了碳材料代替純鋰做為負極

27 Lithium Ion Battery Development Attempts to develop recharageable lithium batteries followed in the eithties, but failed due to safty problems The lithium ion battery has a slightly lower energy density than lithium metal, but it is much safer. Introduced by Sony 1991

28 Lithium secondary battery A chemical intercalation reaction Intercalation is the reversible inclusion of a molecule between two other molecules Ex: graphite intercalation compounds Armand, Nature, 2001

29 The operation principle of a Li-Ion battery

30 Intercalation process 充電時, 鋰離子從 LiCoO2 脫出 Co+3 氧化為 Co+4; 放電池鋰離子則嵌入 LiCoO2, 則 Co+4 Co+3 換句話說, 充電時由外界輸入能量而迫使鋰離子由低能量之正極材料往負極材料移動, 而成為能量較高之狀態 ; 而放電時, 鋰離子將會自然地由高能量之負極材料移動至較低能量之正極材料之中, 並同時對外釋出能量

31 Overall reaction of Li-ion battery P. G. Bruce, B. Scrosati, J. M. Tarascon, Angew Chem. Int. Ed., 2008, 47, 2930 ΔV Charging Co+3->Co+4 discharging Co+4->Co+3

32 Rocking-chair tecnology

33 Combination of positive materials and negative materials for Lithium batteries Armand, Nature, 2001

34 Voltage of a cell

35 Capacity

36 Cathode materials

37 Cathode materials in Lithium-ion batteries

39 锂离子电池结构正极正极物质 : 钴酸锂 + 碳黑 +PVDF 正极基体 : 铝箔 ( 约 0.020mm 厚 ) 正极集流体 : 铝带 ( 约 0.1mm 厚 ) Editor: Frank Veken_Baowang

40 Cathode Materials Challenges The most desirable cathode materials are strong oxiding agents that can react with and decompose organic electrolytes In extreme cases, problems with internal shorts or improper voltages can trigger exthermic reactions, leading to thermal runaway and catastropic falure

41 Anode materials: Carbon However, its theoretical capacity (LiC6) is only 372 mahg -1

42 Anode materials

43 锂离子电池结构负极负极集流体 : 镍带 ( 约 0.07mm 厚 ) 负极基体 : 铜箔 ( 约 0.015mm 厚 ) 负极物质 : 石墨 +CMC+SBR

44 Li-alloy based anode materials for Li secondary batteries CSR, 2010

45 Anode capacity for total specific capacity Electro Acta

46 隔離膜材質 : 單層 PE( 聚乙烯 ) 或者三層複合 PP( 聚丙烯 ) +PE+PP 厚度 : 單層一般為 0.016~0.020mm 三層一般為 0.020~0.025mm

47 電解液性質 : 無色透明液體, 具有較強吸濕性應用 : 主要用於可充電鋰離子電池的電解液, 只能在乾燥環境下使用操作 ( 如環境水分小於 20ppm 的手套箱內 ) 規格 : 溶劑組成 DMC:EMC:EC =1:1:1 ( 重量比 ) LiPF6 濃度 1mol/l 品質指標 : 密度 (25 )g/cm3 1.23±0.03 水分 ( 卡爾費休法 ) 20ppm 游離酸 ( 以 HF 計 ) 50ppm 電導率 (25 ) 10.4±0.5 ms/cm

48 Electrolyte challenges: Liquid electrolyte (LiPF6/EC+DMC) Problems: leakage, non-flexibility of the cells, side reactions with charged electrodes Explosions

49 新型電解液非水溶液系, 如離子溶液化學和電化學穩定性好, 與電極材料和集流體以及隔離膜不發生反應較高的離子導電性沸點高冰點低 ( 在 -40~70C 保持液態 ) 高熱穩定性較寬電化學視窗

Lithium-Ion and Lithium-Ion Polymer Batteries Great energy-to-weight ratio (~160 Wh/kg compared to 30-80 Wh/kg in NiMH) No memory effect. Slow self-discharge rate.

50 Lithium-Ion and Lithium-Ion Polymer Batteries Great energy-to-weight ratio (~160 Wh/kg compared to Wh/kg in NiMH) No memory effect. Slow self-discharge rate. Battery will degrade from moment it is made. Protection circuits are required to protect the battery. Li-Ion Polymer batteries are significantly improved. Higher energy density. Lower manufacturing costs More robust to physical damage Can take on more shapes.

51 Comparison of the different battery technologies in terms of volumetric and gravimetric energy density. Armand, Nature, 2001

Disadvantages of Li-Ion EXPENSIVE -- 40%

DELICATE -- battery temp must be monitored

batteries in bulk (which also raises the

53 Disadvantages of Li-Ion EXPENSIVE -- 40% more than NiCd. DELICATE -- battery temp must be monitored from within (which raises the price), and sealed particularly well. REGULATIONS -- when shipping Li-Ion batteries in bulk (which also raises the price). Class 9 miscellaneous hazardous material UN Manual of Tests and Criteria (III, 38.3)

54 Schematic drawing of Li-ion batteries

55 Types of lithium-ion batteries 圓柱型 :5 位數前兩位為直徑, 後兩位數為高度型電池, 直徑 18mm, 高度 65mm

56 Types of lithium-ion batteries 方形 : 六位數前兩位電池厚度中間兩位為電池寬度, 後面兩位為電池長度 : 厚度 8mm 寬度 :34mm 長度 48mm

24-2_cover_OK

24-2_cover_OK 2 08 Flexible All Solid State Thin Film Li-ion Battery 1 1 2 1 1 2 ( 300Wh/kg) (3.4~3.8 V) ( 1000 cycles) (LiCoO 2 ) (LiPON) (Mica) 26mAhcm -2 mm -1 30 85% LED Abstract With the ever-changing technology,