课程大纲

COURSE SYLLABUS

课程代码/名称

Course Code/Title

MSE5022 电解质基础 Fundamentals of Electrolytes

课程性质

Compulsory/Elective

专业选修课

课程学分/学时

Course Credit/Hours

3/48

授课语言

Teaching Language

英语/English

授课教师

Instructor(s)

邓永红副教授

是否面向本科生开放

Open to undergraduates

or not

否

先修要求

Pre-requisites

MSE301 材料化学；MSE306 材料测试分析技术

教学目标

Course Objectives

让学生理解电解质是如何工作的，为如何设计高性能电解质奠定基础。 Let students know how electrolyte

additives work in Li-ion batteries，and how to design the electrolytes with high performances

教学方法

Teaching Methods

本课程分课堂讲解、师生讨论、课后文献查找等环节。通过理论联系实际的训练，让同学展示自己对重要知识点的理

解和掌握程度

The course is achieved by teaching in classroom, discussing between the teacher and students, and

looking up references after school. Training the students by linking theory with practice, and then let

them show their understanding and mastering degree on important knowledge points

10.

教学内容

Course Contents

Section 1

Introduction and Scope

Electrochemistry Basics：

Faraday，

Nernst

Volta： What is Battery？

Why a Battery Is Complicated

Battery basics: E=C * V

Components and system：

What determines electrode potential？

What determines capacity？

What determines energy？

What if“Moore’s Law” is obeyed？

The Attraction of “Lithium” and Its Challenge

Why Lithium？

The energy density of possible metal anodes (compare Na, Be, Mg,

Al etc)

The ultimate anode

The challenge：

Reactivity and passivation

Interphase (SEI)

Dendrite and dead Li

The first fiasco of Li-metal batteries (Moli, 1988)

From “Lithium” to “Lithium Ion”

The intercalation Bypass

“Host-guest” chemistry (1960 concepts; 1987 Nobel prize)

Electrochemical extension of “ Host-guest ” chemistry ： dual-

intercalation battery concept （Armand 1980）

Whittingham (1976?):

chalcogenides (TiS2); stable electrochemical system: Li/TiS2;

unstable vs. moisture; low potential (2 V batteries)

35 yrs later the battery still works

Goodenough (1980)

Oxides replacing chalcogenides: stable vs moisture; high potential (4

V batteries)

LCO (1980); LMO (with Thackeray, 1985?); LiFePO4 (with Padhi,

1997)

Scrosati assembled the 1st LIB by concept: Transition oxides as both

electrodes; 2 V

Asahi Kansei assembled the 1st modern LIB (1986): LCO cathode;

petroleum coke anode; PC electrolyte

Sony commercialize the 1st modern LIB (1990)

Section 2

Fundamentals of Battery Electrolytes

Electrolyte separates cathode and anode as ionic conductor:

Conducts ionic current

Insulates electron transport

Facilitates mass transport

Electrolyte requirements: ion conductor; electron insulator; medium

for mass transport; electrochemically stable on both cathode and anode

Thermodynamic stability vs kinetic stability (interphase)

Electrolyte is ionic conductor, therefore a salt needs to be in

dissociated state, so that cation and anion can move

Ionic liquid (molten salt)

Electrolyte solution: solvent molecules dissolve cations and anions

Most electrolytes are liquid: good contact at interfaces

HOMO/LUMO of electrolytes vs. redox potential of electrodes

Lower LUMO: resistance against reduction

Higher HOMO：resistance against oxidation

Section 3

Electrolyte Components

Solvents: high dielectric constant (ability to dissolve salt into separate

ions); low viscosity （high transport rate and high ionic mobility）, stability

against reduction and oxidation at electrodes (ether: high stability vs

reduction; esters: high stability vs. oxidation)

Propylene Carbonate (PC)

Ethylene Carbonate (EC)

Linear Dialkyl Carbonates

Other new solvents

Salts ： cations of interest to cell chemistry (eg., Li+ for Li-based

batteries); anions with high stability with other electrolyte and cell

components (especially stable against oxidation); high dissociation constant

Lithium Perchlorate (LiClO4)

Lithium Hexafluoroarsenate (LiAsF6)

Lithium Tetrafluoroborate (LiBF4)

Lithium Trifluoromethanesulfonate (LiTf)

Lithium Bis(trifluoromethanesulfonyl)imide (LiIm) and Its

Derivatives

Lithium Hexafluorophosphate (LiPF6)

Other new salts

Functional Additives

S-containing Additives

P-containing Additives

Si-containing Additives

Other New Additives

Section 4

Electrolyte Bulk Properties

4.1. Ion Transport

4.2. Li+-Solvation

4.3. Li+−Solvent Interaction in Electrolyte Solutions

4.4. Li+-Solvates in Concentrated Electrolytes

Section 5

Interface & Interphase

5.1 Electrolyte/Anode Interface: SEI

Passivation on Lithium Anode

Electrolyte/Carbonaceous Anode Interface

Exfoliation and Irreversible Capacities on a Carbonaceous Anode

Mechanism of SEI Formation

5.2 Electrolyte/Cathode Interface: CEI

Passivation Film on a Cathode

Mechanism of SEI Formation

5.3 Breakdown of Surface Layer

5.4. Passivation of Current Collector

Section 6

6. Chemical and Thermal Stability/Safety of Electrolytes

Long-Term Stability of Electrolytes at Elevated Temperatures

Stability of the SEI or Surface Layer at Elevated Temperatures

Thermal Safety of Electrolytes against Abuse

Degradation Mechanisms

Electrolyte Components to Suppress Degradations

Chemical and Thermal Degradations

Degradations with Anode

Degradations with Cathode

Degradations with Aluminum Substrate

Section 7

Characterization

X-rayPhotoelectron Spectroscopy (XPS)

GC-MS/ LC-MS spectroscopy

Advanced Characterization and Imaging

Ellipsometry and Sum-Frequency Generation Spectra

Electron Microscopes

Acoustics

Neutron-Based Techniques

Fluorescence

Electrochemical Quartz Crystal Microbalance

Scanning Probe Microscopy

Section 8

Novel Electrolyte Systems

8.1. Problems Facing State-of-the-Art Electrolytes

8.2.1.Anode: SEI Modification

8.2.3. Cathode: Overcharge Protection

8.3. New Electrolyte Components

8.3.1. Nonaqueous Solvents

8.3.2. Lithium Salts

8.4. Novel Electrolytes with a Wide Temperature

Range

8.4.1. Low-Temperature Performance

8.4.2. High-Temperature Performance

8.5. Electrolytes of Low Flammability

8.6. Polymer and Polymer Gel Electrolytes

8.6.1. Solid Polymer Electrolyte

8.6.2. Gel Polymer Electrolyte

11.

课程考核

Course Assessment

课程考核分为三部分：期末考查：50%；其中考查 20%；考勤、作业、课堂表现 30%。

Three parts for course assessments: Final Assessment: 50% ； Middle Assessment: 20% ； Attendance ，

Assignments and Classroom Performance: 30%

12.

教材及其它参考资料

Textbook and Supplementary Readings

1. Martin Winter, Brian Barnett, and Kang Xu. Before Li Ion Batteries. Chem. Rev. 2018, 118, 11433−11456

2. Kang Xu. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114, 11503 –

11618.

3. Nonaqueous Liquid Electrolytes for Lithium-Based Rechargeable Batteries. Chem. Rev. 2004, 104, 4303-

4417

4. Y.H. Deng*et.al. How electrolyte additives work in Li-ion batteries, Energy Storage Materials, 2018, DOI:

10.1016/j.ensm

5. John O ’ M., Bockris and Amulya K.N. Reddy. 《 Modern Electrochemistry 1 ： Ionics 》 , Kluwer

Academic/Plenum

Publishers, 1998.6. ISBN-10：0306455552