LTO The new kid on the Liion battery

锂电后起之秀–钛酸锂 LTO – The new kid on the Li-ion battery block 薛嘉渔 首席科学家 山东玉皇新能源科技有限公司 December. 2017 Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

CONTENTS 目 录 1 动力电池类型 Types of power Li-ion batteries 2 钛酸锂电池是一个优秀的电化学体系 3 钛酸锂电池的应用市场在哪里？ LTO battery is an excellent EC system Where’s the applications for LTO battery?

1 动力电池类型 Types of power Li-ion batteries

Requirement of Li-ion cells for x. EV 1. Safety 2. Consistency (or Reliability) 3. Long cycle life (10 -15 yrs? ) 4. High power density (HEV) 5. High energy density (BEV) 6. Low cost (5 -10% lower/year? ) 7. High & low temperature performance (-40 to 65 o. C ) Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Aluminum cased prismatic cells for x. EV Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Aluminum cased Li-ion cell for x. EV Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Pouch prismatic cells for x. EV Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Pouch prismatic cells for x. EV Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

How the cell fails (the nightmare for LIB engineers)? Abnormal amount of heat generated internally in the cell mostly from graphite anode could lead to fire or explosion! Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

The expansion/contraction of the LIB 起始状态 Initial state 经长期循环 After extensive cycling The internal mechanical stress of electrodes caused by charging/discharging graphite leads to electrode disconnection in the cell! Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

2 钛酸锂电池是一个优秀的电化学体系 LTO battery is an excellent EC system

Brief history of LTO v In 1971, spinel type Li 4 Ti 5 O 12 or LTO was first reported by Deschanvres et al. Deschanvres A, Raveau B, Sekkal Z. Mise en evidence cristallographique d'une nouvelle solution solide de type spinelle Li 1 Ti 2, O 4(0≤x≤ 0. 33) [J]. Mat. Res. Bull. , 1971, 6(8) : 699 -704. v In 1989, Colbow et al. had studied more than its structural properties but also the possibility of using LTO as an electrochemical material. Colbow K M, Dahn J R, Haering R R. Structure and Electrochemistry of the Spinel Oxides Li. Ti 2 O 4 and Li 4/3 Ti 5/3 O 4 [J]. J. Power Sources, 1989, 26(3 -4): 397 -402. v In 1995, Ohzuku et al. referred the LTO as a “zero strained material”. Ozuku T, Ueda A, Yamamoto N. Zero-Strain Insertion Material of Li[Li 1/3 Ti 5/3]O 4 for Rechargeable Lithium Cells[J]. J. Electrochem. Soc. , 1995, 142(5): 1431 -1435. v ……. . Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

How the LTO chemistry works? Spinel = AM 2 O 4 or (AM 2 O 4)x 3 = A 3 M 6 O 12 Li 4 Ti 5 O 12 6 Li+ move from 8 a to 16 c Space group: Fd 3 m a = 0. 836 nm 5 Ti 4+/1 Li+ in 16 d site or Oh Li+ in 8 a site or Td (Disch) Li+ in 16 c site or Oh (Ch) Chemical formula: Li 3(Li 1 Ti 5)O 12 Discharge state: [Li+3]8 a[Li+Ti 4+5]16 d[O 2 -12 ]32 e Charge balanced: Charge state: [Li+6]16 c[Li+Ti 3+3 Ti 4+2]16 d[O 2 -12 ]32 e Li+3(Li+1 Ti 4+5)O 2 -12 adisch=0. 836 nm; a. Ch=0. 837 nm “Zero strained” crystal lattice Theoretical capacity: 175 m. Ah/g Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Is graphite the angel / devil in the Li-ion cells? Graphite is the angel! 1. OK low T performance 2. OK cycle life 3. OK charge/discharge rate 4. Cell expansion 5. High energy density (E. D. ) Graphite is the devil ! LTO shows just the opposite of graphite : - Due to SEI (1 -3) - no SEI (1 -3) - Intrinsic layer expansion (4) - “Zero stress” crystal lattice (4) - Intrinsic E. P. ≈ Li 0 (5) - E. P. =1. 55 V , safe but less E. D. ! Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Pro’s & Con’s of LTO Safest Anode Longest cycle life Con’s of LTO - Low energy density - High material cost ? Targeted market & IP Cost effective High rate capability LTO Low/high T performance Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC) - Cell gassing (know-how)? - Market is not obvious? (educate the consumers)

Price of various anode materials Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Supply/demand world of anode materials Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Road to glory? v How to achieve a high energy cell? A 3. 5 V LTO cell can be built by using § 5 V cathode (Li. Ni 0. 5 Mn 1. 5 O 4, LCP, LCMP, … etc. ) § stable electrolyte systems (PC? new Li salt? ) § anti-oxidation separators (ceramic? ) § …… Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Novel Anode Materials Li 2 Ti. Si. O 5 (LTSO) - First reported by: S. Patoux & C. Masquelier, Chem. Mater. , 2002, 14, 5057 -68. - Y. Y. Xia et al. , Energy & Environ. Sci. , 2017, Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Electrochemical Properties of Li 2 Ti. Si. O 5 Voltage range (V) Capacity (m. Ah/g) (1) 3. 0 - 0. 2 210 (2) 3. 0 – 0. 1 240 (3) 3. 0 – 0. 0 308 Li-insertion Mechanism: Conversion / Solid Solution Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Full Cell Performance of LTSO / NCM The full battery delivered an average working voltage of 3. 25 V and a practical specific energy of 130 Wh/kg can be expected, which is larger than 75 Wh/kg of commercialized Li. Mn 2 O 4/Li 4 Ti 5 O 12 battery. Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

3 钛酸锂电池的应用市场在哪里？ Where’s the applications for LTO battery?

高倍率 Where’s the market for LTO batteries? 3. 1 Energy Storage（储能） 3. 1. 1 Renewable Energy（可再生能源） - PV（太阳能） - Wind farm（风能） 3. 1. 2 Residential & Business （居民小区/商业区） 高安全 长寿命 - uninterrupted power supplies (UPS)（不间断电源） in banks, hospitals, database, office buildings & residential compounds（银行、医院、数据中心、办公楼、小区等） - family energy storage (FES)（家庭储能） Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC) 长寿命 高低温

Where’s the market for LTO batteries? 高安全 大功率 3. 1. 3 Smart Grid （智能电网） - frequency regulation (FR)（调频） - peak shaving (PS)（调峰） 高安全 长寿命 大功率 3. 1. 4 Remote Areas - remote areas（边远地区） - islands（孤岛运作） Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Where’s the market for LTO batteries? 高寒地带 低温 3. 1. 5 Cold region （寒冷地带） - Northern China, Russia, Canada, European countries…. （中国北方、俄国、加拿大、北欧 …） Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC) 长寿命

Where’s the market for LTO batteries? 3. 1. 6 Industrial applications （ 业用途） - warehouse operation, harbor machinery, folk-lift … （仓库管理、叉车、港口机械 …） 高安全 大功率 高安全 长寿命 Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Where’s the market for LTO batteries? 3. 1. 7 Military & space exploring （军事与太空探险） 高安全 高安全 Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Where’s the market for LTO batteries? 3. 2 Transportation（交通） 高安全 高倍率 3. 2. 1 Fixed distance buses （固定距离公交大巴） 3. 2. 2 Consumer vehicles - Logistic & postal cars, （物流车，邮车） … 3. 2. 3 Various Passenger cars (HEV’s) （各种电动、混动乗用车） 高安全 高倍率 Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Where’s the market for LTO batteries? 高安全 China’s LTO x. EV’s （我国的LTO车） 高倍率 长寿命 微宏动力 河北银隆 天津捷威 天康/正道 四川兴能 Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Where’s the market for LTO batteries? Toshiba’s LTO EV’s （东芝的LTO乗用车） 日本东通 推出的Style-D超小型Piana 双座车 采用新日本电池的 7. 2 k. Wh NCM/LTO 电池. - 5分钟充满电 - 无需BMS Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC) 高安全 长寿命

Something else about the LTO tech. v LTO materials & Cells - - Al current collector used for both anode & cathode in the LTO cells ($, wt. ). PC based electrolyte provide better high/low temperature performance LTO cell is anode limited, while a graphite cell is cathode limited. As made LTO materials are hygroscopic (p. H=11 -12). Therefore, LTO cell manufacture is NOT a “drop in” for a conventional graphite cell manufacturing line. Environment, process and production facilities need to be modified accordingly. LTO’s 10 x longer cycle life = 10 x less used batteries (than graphite cells). v LTO Packs - No need for heater (saving on weight, space & money) - No BMS is needed ($, wt. space). Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Something else about the LTO tech. v Applications for safe LTO technology - HEV, Rail way, subway, industrial, ISS (fast charge/discharge) Auto in cold climate (low T performance) Fixed distance Bus (8 yrs service life) Family energy storage system or FESS (safety), Grid (frequency regulation) (fast discharge), ESS for wind & PV (extremely long cycle life). Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)

Thank you for your kind attention! Further readings: 薛嘉� 等， � 酸�� 池技� 及其��� 展� 状，《新材料�� , 》9(2015)12 -17. 薛嘉� ，中国���� 能否走向� 治久安之路？ http: //www. ciaps. org. cn/news/show-htmitemid-14881. html Contact info: sxue 2008@126. com Shandong Yuhuang New Energy Technology Co. , Ltd. (YH NETC)