Regarding sodium ion batteries, you should know...

A dynamic in the Ningde era "triggered" the industry's attention to sodium-ion batteries.

Recently, the chairman of CATL, Zeng Yuqun, revealed at the 2020 annual shareholders meeting that CATL will release sodium batteries around July this year, and further stated that “our technology is developing and sodium-ion batteries have matured”.

Sodium ion battery is a new industry, but it is not a brand new battery technology route. As early as the 1970s, the research on sodium ion batteries was carried out almost synchronously with lithium batteries, but due to the limitations of the research conditions at that time and the market's preference for lithium ion batteries, the research progress of sodium ion batteries was slow.

In recent years, the local supply of raw materials for lithium-ion batteries has been insufficient, and more than 60% of the lithium raw materials used in the production of lithium salt in China need to be imported, which is highly dependent on foreign sources.

The sodium-ion battery has many advantages such as extremely rich reserves, high safety, low cost (large-scale), and support for fast charging, and the market is heating up significantly. Zeng Yuqun once said bluntly, "Sodium chloride (price) can't be fried, there is a lot of salt."

In addition, sodium does not form an alloy with aluminum, and both the positive and negative electrodes can use aluminum foil current collectors to construct bipolar batteries, further reducing cost and weight. At the same time, sodium batteries are highly similar in structure and packaging process to lithium batteries, and the original lithium battery factory can directly produce sodium batteries without major changes.

Based on this, not only the Ningde era, but also many companies at home and abroad have conducted research on sodium batteries and have made good progress.

As of 2020, there are nearly 20 domestic and foreign companies in the industrialization of sodium-ion batteries, including FARADION in the United Kingdom, Natron Energy in the United States, Aquion Energy in the United States, the French NAIADES planning group, Japan's Kishida Chemical, Panasonic, Mitsubishi and other international companies. As well as domestic enterprises such as Zhongke Hai Na, Sodium Innovative Energy, and Xingkong Nadian.

For example, in June 2018, Zhongke Hai Na Technology launched the first domestic low-speed electric car with sodium ion batteries and demonstrated it in the park of the Institute of Physics, Chinese Academy of Sciences. In 2020, Zhongke Haina also developed 10 Ah pouch and 18650 cylindrical batteries based on O3 phase composite cathode materials, with an energy density of 135Wh/kg, a discharge rate that can vary from 1C to 5C, and a capacity retention rate of 90%.

The consensus in the industry is that it has many advantages such as cost and resources. However, sodium-ion batteries are subject to their own material properties. The energy density of the negative electrode is lower than that of graphite materials, and the energy density is at a disadvantage compared with lithium-ion batteries, so it is temporarily unable to replace lithium-ion batteries. The battery has become the mainstream technology in the power field, and it is more of a technical reserve and supplement.

At present, the cell energy density of sodium batteries on the market is generally 100~150Wh/kg. Among the mainstream car-grade power batteries, the energy density of the ternary lifepo4 battery has reached about 250Wh/kg; the energy density of the lithium iron phosphate battery is slightly lower, but it is also about 180Wh/kg.

Compared with lead-acid batteries, in addition to considering the cost of recycling, there is no advantage, and other technical indicators have achieved a comprehensive and substantial surpass.

On the whole, the commercialization of sodium-ion battery technology in China is imperative. Sodium ion battery technology can not only meet the requirements of low cost, long life and high safety performance in the new energy field, but also relieve the anxiety caused by the shortage of lithium resources to a certain extent. It is an important supplement to lithium ion batteries and can gradually replace lead-acid batteries. , Is expected to develop rapidly in many fields such as low-speed electric vehicles, electric boats, home/industrial energy storage, 5G communication base stations, data centers, large-scale access to renewable energy, and smart grids.

At this stage, due to the immature preparation process and production equipment of the sodium battery system, the production efficiency is low, the product consistency is poor, the production yield is not high, and the production cost is significantly higher than that of lithium-ion batteries. The material cost advantage of sodium-ion batteries is temporarily not obvious. .

From the perspective of commercialization progress, internationally, Faradion in the United Kingdom has developed a layered oxide cathode material with a higher specific capacity, and the full battery composed of it can even exceed the lithium iron phosphate battery in the lithium ion battery. The Natron Energy of Novasis Energies, a subsidiary of Stanford, has also successfully developed a sodium-ion battery with PBA as the positive electrode.

In addition to the technology to be disclosed in the Ningde era, the Institute of Physics of the Chinese Academy of Sciences has long established a layout in this field.

The Institute of Physics, Chinese Academy of Sciences has been committed to the development of safe, environmentally friendly, low-cost, high-performance sodium-ion battery technology since 2011, and has obtained 20 patents for core materials (3 patents have been authorized by the United States, Japan and the European Union). The Cu-based layered oxide cathode materials and low-cost anthracite-based anode materials developed with independent intellectual property rights are all international firsts.

In 2017, relying on the sodium-ion battery technology of the Institute of Physics of the Chinese Academy of Sciences, the first domestic Zhongke Hai sodium focused on the research and development and production of sodium-ion batteries was established, and orderly promoted the scale-up preparation and production of key materials, battery cell design and development, and modules Integration and management.

Its technical team is led by Chen Liquan, academician of the Chinese Academy of Engineering, Hu Yongsheng, a researcher at the Institute of Physics, Chinese Academy of Sciences, and others. Among them, Chen Liquan is Zeng Yuqun’s doctoral supervisor.

At present, Zhongke Haina has built a 100-ton pilot line for sodium ion battery positive and negative materials and MW⋅h-level battery core wires, and has developed soft packs, aluminum shells and cylindrical batteries. At present, its sodium ion battery production capacity can reach up to 300,000 pcs/month, and its products include cylindrical batteries and soft-packed batteries.

It is necessary to point out that the sodium-ion battery market is heating up, and young students, researchers and business people continue to emerge in this research field. The market urgently needs a book on sodium-ion batteries as a booster to acquire more systems and more cutting-edge knowledge. , To make more innovative and in-depth research results to provide theoretical and technical support for the development and application of sodium ion batteries.

The team of the Institute of Physics of the Chinese Academy of Sciences led by Academician Chen Liquan and Hu Yongsheng organized and wrote a professional book on sodium ion battery science and technology-"Sodium ion battery science and technology".

This book brings together the research progress made by the team of the Institute of Physics of the Chinese Academy of Sciences in the basic research, development and engineering exploration of sodium-ion batteries in the past ten years, and gathers the outstanding achievements of domestic and foreign experts and scholars in the field of sodium-ion battery technology in the past four decades. Summarize the current research status of sodium ion batteries systematically, focus on discussing the key issues of sodium ion batteries, and focus on looking forward to the development trend of sodium ion batteries.

According to reports, the book focuses on the development history, working principles, performance characteristics and basic concepts of sodium-ion batteries, and discusses the preparation methods, physical and chemical properties, and sodium ion batteries of cathode materials, anode materials, liquid electrolytes, solid electrolytes and inactive materials. The impact of ion battery performance is reviewed, and the application of advanced characterization technology and theoretical calculation simulation in the research of sodium ion battery is reviewed, and the manufacturing process, failure analysis, cost estimation and industrialization status of sodium ion battery are described separately.

In addition, the book gathers the latest scientific and technological achievements and related technologies of domestic and foreign researchers, and reflects the current development and research trend of sodium ion batteries. It is the basic theoretical research and research of materials, physics, chemistry, electrochemistry, chemical engineering, energy and other disciplines. The integrated reflection of the cutting-edge application technology contributes to the exploration of the technology and application of sodium batteries in the field of energy storage and power batteries.

At present, the second printing of "Sodium Ion Battery Science and Technology" is now on sale and can be purchased by scanning the code.

Science Mall (Science Press)

Book catalog

table of Contents

Series Preface

Preface

Chapter 1 Introduction to Sodium Ion Batteries 1

1.1 Overview 2

1.2 The birth and development of sodium ion batteries 4

1.3 The working principle and characteristics of sodium ion battery 7

1.3.1 The working principle of sodium ion battery 7

1.3.2 Characteristics of sodium ion battery 9

1.4 The basic concept of sodium ion battery 13

References 17

Chapter 2 Cathode Materials for Sodium Ion Batteries 19

2.1 Overview 20

2.1.1 The crystal structure of a typical cathode material 23

2.1.2 Common synthesis methods for cathode materials 27

2.2 Oxide cathode materials 31

2.2.1 Layered oxide cathode materials 34

2.2.2 Other oxide cathode materials 51

2.2.3 Some basic scientific issues of layered oxide cathode materials 55

2.3 Polyanionic cathode materials 79

2.3.1 Phosphate 81

2.3.2 Sulfate 86

2.3.3 Silicate 90

2.3.4 Borate 90

2.3.5 Mixed polyanionic compounds 92

2.4 Prussian blue cathode materials 98

2.4.1 Application of Prussian Blue in non-aqueous sodium ion batteries 99

2.4.2 The application of Prussian blue in water-based sodium ion batteries 105

2.5 Organic cathode materials 108

2.5.1 Conductive polymers 110

2.5.2 Organic conjugated carbonyl compounds 110

References 112

Chapter 3 Anode Materials for Sodium Ion Batteries 124

3.1 Overview 125

3.2 Carbon-based anode materials 127

3.2.1 Types and development history of carbon materials 127

3.2.2 Graphite-like carbon materials 128

3.2.3 Amorphous carbon materials 134

3.2.4 Nano-carbon materials 137

3.2.5 Characteristic analysis of charge and discharge curve of carbon anode 139

3.2.6 Microstructure control of carbon materials 146

3.2.7 Evaluation of the electrochemical performance of carbon materials 155

3.3 Titanium-based anode materials 158

3.3.1 Na2Ti3O7 158

3.3.2 Li4Ti5O12 159

3.3.3 Na0.66[Li0.22Ti0.78]O2 160

3.3.4 Na0.6[Cr0.6Ti0.4]O2 161

3.3.5 NaTiOPO4 162

3.3.6 NaTi2(PO4)3 163

3.4 Organic anode materials 163

3.4.1 Common organic anode materials 164

3.4.2 Sodium storage mechanism of conjugated carbonyl compounds 166

3.5 Alloys and other anode materials 168

3.5.1 Alloy materials 168

3.5.2 Other materials 172

3.5.3 Common improvement strategies for alloys and other materials 172

References 175

Chapter 4 Liquid Electrolytes for Sodium Ion Batteries 180

4.1 Overview 181

4.2 Basic physical and chemical properties of electrolyte 183

4.2.1 The nature of transmission 184

4.2.2 Chemical and electrochemical stability 186

4.2.3 Thermal stability 189

4.2.4 Spectroscopy technology and electrolyte physical and chemical properties 190

4.3 Organic solvents 191

4.3.1 Carbonate solvents 192

4.3.2 Ether solvents 195

4.3.3 Other solvents 196

4.3.4 Selection of organic solvent 200

4.4 Electrolyte salt 206

4.4.1 Inorganic sodium salt 206

4.4.2 Organic Sodium Salt 207

4.4.3 Other sodium salts 208

4.4.4 Selection of sodium salt 210

4.5 Interface and organic electrolyte additives 211

4.5.1 The interface between the electrolyte and the electrode material 211

4.5.2 Organic electrolyte additives 221

4.6 New electrolyte system and application 230

4.6.1 Aqueous electrolyte 230

4.6.2 High salt concentration electrolyte 232

4.6.3 Ionic liquid electrolyte 236

4.6.4 Non-flammable electrolyte 238

References 240

Chapter 5 Solid Electrolytes for Sodium Ion Batteries 245

5.1 Overview 246

5.2 Characterization of basic physical and chemical properties of solid electrolyte 249

5.2.1 Ionic conductivity 249

5.2.2 Ion diffusion activation energy 251

5.2.3 Ion migration number 251

5.2.4 Electrochemical window 252

5.3 Inorganic solid electrolyte 253

5.3.1 Ion diffusion mechanism 254

5.3.2 Oxide solid electrolyte 255

5.3.3 Sulfide solid electrolyte 261

5.3.4 Other inorganic solid electrolytes 265

5.4 Polymer electrolyte 265

5.4.1 Ion transport mechanism 267

5.4.2 Polyethylene oxide solid polymer electrolyte 268

5.4.3 Non-polyethylene oxide based solid polymer electrolyte 275

5.4.4 Gel polymer electrolyte 279

5.5 Composite solid electrolyte 285

5.5.1 Inert nanoparticle-polymer composite solid electrolyte 285

5.5.2 Active inorganic solid electrolyte-polymer composite solid electrolyte 286

5.5.3 Other types of composite solid electrolytes 287

5.6 Interfaces in solid sodium batteries 288

5.6.1 Interface issues in solid-state batteries 289

5.6.2 Interface modification of solid-state batteries 290

References 294

Chapter 6 Inactive Materials for Sodium Ion Batteries 300

6.1 Overview 301

6.2 Diaphragm material 302

6.2.1 Common diaphragm materials and their modifications 303

6.2.2 New diaphragm materials 304

6.3 Binder material 308

6.3.1 Common adhesive materials 309

6.3.2 The effect of binder on the electrochemical performance of electrode materials 311

6.4 Conductive agent materials 315

6.5 Current collector material 317

6.5.1 Common current collector materials 317

6.5.2 New current collector materials 318

References 323

Chapter 7 Sodium Ion Battery Characterization Techniques 326

7.1 Overview 327

7.2 Diffraction technology 329

7.2.1 X-ray diffraction technique 329

7.2.2 Synchrotron radiation X-ray diffraction technology 334

7.2.3 Neutron Diffraction Technology 337

7.2.4 Pair distribution functions 340

7.3 Transmission electron microscopy technology 341

7.3.1 Transmission electron microscopy 341

7.3.2 Scanning Transmission Electron Microscopy 343

7.3.3 X-ray energy spectrum and electron energy loss spectrum analysis 344

7.4 Solid-state nuclear magnetic resonance spectroscopy technology 346

7.5 X-ray absorption spectroscopy technology 349

7.6 Surface analysis technology 352

7.6.1 X-ray photoelectron spectroscopy technology 352

7.6.2 Atomic Force Microscopy 355

7.7 Electrochemical characterization techniques 356

7.7.1 Linear Potential Sweep Method 356

7.7.2 Constant current intermittent titration and constant potential intermittent titration technology 358

7.7.3 Electrochemical impedance spectroscopy technology 362

References 365

Chapter 8 Theoretical Calculation and Simulation of Sodium Ion Battery 369

8.1 Overview 370

8.2 Introduction to theoretical calculations and simulation methods based on quantum mechanics 371

8.2.1 Density functional theory

8.2.2 Hybrid functional/DFT+U method and DFT-D