Technological improvements in rechargeable solid-state batteries are being driven by an ever-increasing demand for portable electronic devices. Lithium-ion batteries are the systems of choice, offering high energy density, flexible and lightweight design, and longer lifespan than comparable battery technologies. We present a brief historical review of the development of lithium-based rechargeable batteries, highlight ongoing research strategies, and discuss the challenges that remain regarding the synthesis, characterization, electrochemical performance and safety of these systems.

Issues and challenges facing rechargeable lithium batteries

The challenges for further development of Li rechargeable batteries for electric vehicles are reviewed. Most important is safety, which requires development of a nonflammable electrolyte with either a larger window between its lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) or a constituent (or additive) that can develop rapidly a solid/ electrolyte-interface (SEI) layer to prevent plating of Li on a carbon anode during a fast charge of the battery. A high Li-ion conductivity (σ Li > 10 ―4 S/cm) in the electrolyte and across the electrode/ electrolyte interface is needed for a power battery. Important also is an increase in the density of the stored energy, which is the product of the voltage and capacity of reversible Li insertion/extraction into/from the electrodes. It will be difficult to design a better anode than carbon, but carbon requires formation of an SEI layer, which involves an irreversible capacity loss. The design of a cathode composed of environmentally benign, low-cost materials that has its electrochemical potential μ C well-matched to the HOMO of the electrolyte and allows access to two Li atoms per transition-metal cation would increase the energy density, but it is a daunting challenge. Two redox couples can be accessed where the cation redox couples are "pinned" at the top of the O 2p bands, but to take advantage of this possibility, it must be realized in a framework structure that can accept more than one Li atom per transition-metal cation. Moreover, such a situation represents an intrinsic voltage limit of the cathode, and matching this limit to the HOMO of the electrolyte requires the ability to tune the intrinsic voltage limit. Finally, the chemical compatibility in the battery must allow a long service life.

Challenges for Rechargeable Li Batteries

Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid–solution range. The solid–solution range, which is...

The Li-ion rechargeable battery: a perspective.

2.1. Solvents 4307 2.1.1. Propylene Carbonate (PC) 4308 2.1.2. Ethers 4308 2.1.3. Ethylene Carbonate (EC) 4309 2.1.4. Linear Dialkyl Carbonates 4310 2.2. Lithium Salts 4310 2.2.1. Lithium Perchlorate (LiClO4) 4311 2.2.2. Lithium Hexafluoroarsenate (LiAsF6) 4312 2.2.3. Lithium Tetrafluoroborate (LiBF4) 4312 2.2.4. Lithium Trifluoromethanesulfonate (LiTf) 4312 2.2.5. Lithium Bis(trifluoromethanesulfonyl)imide (LiIm) and Its Derivatives 4313

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Nonaqueous liquid electrolytes for lithium-based rechargeable batteries.

In the previous paper Ralph Brodd and Martin Winter described the different kinds of batteries and fuel cells. In this paper I will describe lithium batteries in more detail, building an overall foundation for the papers that follow which describe specific components in some depth and usually with an emphasis on the materials behavior. The lithium battery industry is undergoing rapid expansion, now representing the largest segment of the portable battery industry and dominating the computer, cell phone, and camera power source industry. However, the present secondary batteries use expensive components, which are not in sufficient supply to allow the industry to grow at the same rate in the next decade. Moreover, the safety of the system is questionable for the large-scale batteries needed for hybrid electric vehicles (HEV). Another battery need is for a high-power system that can be used for power tools, where only the environmentally hazardous Ni/ Cd battery presently meets the requirements. A battery is a transducer that converts chemical energy into electrical energy and vice versa. It contains an anode, a cathode, and an electrolyte. The anode, in the case of a lithium battery, is the source of lithium ions. The cathode is the sink for the lithium ions and is chosen to optimize a number of parameters, discussed below. The electrolyte provides for the separation of ionic transport and electronic transport, and in a perfect battery the lithium ion transport number will be unity in the electrolyte. The cell potential is determined by the difference between the chemical potential of the lithium in the anode and cathode, ∆G ) -EF. As noted above, the lithium ions flow through the electrolyte whereas the electrons generated from the reaction, Li ) Li+ + e-, go through the external circuit to do work. Thus, the electrode system must allow for the flow of both lithium ions and electrons. That is, it must be both a good ionic conductor and an electronic conductor. As discussed below, many electrochemically active materials are not good electronic conductors, so it is necessary to add an electronically conductive material such as carbon * To whom correspondence should be addressed. Phone and fax: (607) 777-4623. E-mail: stanwhit@binghamton.edu. 4271 Chem. Rev. 2004, 104, 4271−4301

http://www.chemie.uni-regensburg.de/Anorganische_Chemie/Vortrag/StudentenWS06-07/Vortrag_Amereller.pdf

Lithium Batteries and Cathode Materials

LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density

LixCoO2 (0<x≤1): A new cathode material for batteries of high energy density

Impurity levels of iron-group ions in TiO2(II)

Insertion compounds contain a mobile cation of variable concentration over a wide range of solid solution. Charge compensation is achieved by a variation of mobile-electron concentration in the host matrix. Such mixed ionic/electronic conductors are of practical interest as electrodes in secondary batteries and electrochromic displays. Oxides containing transition-metal ions in unusually high valence states can be prepared by room-temperature extraction of mobile cations from such structures. Some properties of the systems Li1-yCoO2 and Na1-yCoO2 are presented.

https://iopscience.iop.org/article/10.7567/JJAPS.19S3.305/pdf

Solid-Solution Oxides for Storage-Battery Electrodes

Lithium (Li)-ion materials such as LiCoO2 and (Li3PO4)-N (LiPON) are used in Li-ion all-solid-state batteries, and are now expected to be used as ion-electron hybrid materials to create a new degree of freedom in future integrated circuits. We fabricated thin-film devices on the basis of LiCoO2/LiPON/Cu and ultrathin titanium oxide (TiOx) to demonstrate their new type of resistance change mechanism and characteristics. Multi-level resistance changes promising as synaptic plasticity were obtained, and the resistance properties enable neuromorphic computing to enter a new era. 

K. Mizushima

Papers

LixCoO2 (0<x<-1): A new cathode material for batteries of high energy density

LixCoO2 (0<x≤1): A new cathode material for batteries of high energy density

Impurity levels of iron-group ions in TiO2(II)

Solid-Solution Oxides for Storage-Battery Electrodes

Lithium-ion-based resistive devices of LiCoO2/LiPON/Cu with ultrathin interlayers of titanium oxide for neuromorphic computing