Insertion Material for Lithium-Ion Batteries

Thus we have succeeded in preparing the target material of LiAl1/4Ni3/402 (.R3m), which is a solid solution of a-LiA102 and LiNi02 (R3m) in a ratio of 1 3. 

8 An Innovative LiAl1/4Ni3/402 Insertion Material for Lithium-Ion Batteries 

150mAhg l based on weight of LiAllrtNi3/402, then discharged to 2.5 V. 

The X-ray diffraction examinations of Li, (Al1/4Ni3/402 indicate that the reaction proceeds topotactically in a single phase over the entire range, called a singlephase reactions, as shown in Fig. 12. Gen- 

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Of these requirements (1) - (4) relating to the energy density and requirements (8) and (10) associated with safety are most important behavior criteria for insertion materials for lithium-ion batteries, even in basic research. 

R-h Zeng, X-p Li, Y-c Qiu et al (2010) Synthesis and properties of a lithium-organie coordination compoimd as lithium-inserted material for lithium ion batteries. Electrochem Commun 12(9) 1253-1256... 

The goal in this section is to show the possibility of material design based on an insertion scheme for lithium-ion batteries. In Sec. 2.2 candidate materials for ad-... 

Kumar TP, Ramesh R, Lin YY, Fey GTK (2004) Tin-filled carbon nanotubes as insertion anode materials for lithium-ion batteries. Electrochemistry Communications 6 520-525. 

ZnO displays similar redox and alloying chemistry to the tin oxides on Li insertion [353]. Therefore, it may be an interesting network modifier for tin oxides. Also, ZnSnOs was proposed as a new anode material for lithium-ion batteries [354]. It was prepared as the amorphous product by pyrolysis of ZnSn(OH)6. The reversible capacity of the ZnSn03 electrode was found to be more than 0.8 Ah/g. Zhao and Cao [356] studied antimony-zinc alloy as a potential material for such batteries. Also, zinc-graphite composite was investigated [357] as a candidate for an electrode in lithium-ion batteries. Zinc parhcles were deposited mainly onto graphite surfaces. Also, zinc-polyaniline batteries were developed [358]. The authors examined the parameters that affect the life cycle of such batteries. They found that Zn passivahon is the main factor of the life cycle of zinc-polyaniline batteries. In recent times [359], zinc-poly(anihne-co-o-aminophenol) rechargeable battery was also studied. Other types of batteries based on zinc were of some interest [360]. 

Figures 13 and 14 display the discharge processes for the two kinds of lithium battery. During discharge at the anode the lithium ions are formed from the lithium metal or are released from an Li,A, B < host material at the cathode the lithium ions are inserted into the void spaces of the structure of the A B insertion material. The lithium-ion battery behaves almost like a concentration cell lithium ions move from a lithium-rich source toward the cathode, which acts as sink, while electrons flow through the external circuit from anode to the cathode.

Silicon can exist in two states crystalline and amorphous. As negative electrode materials for lithium-ion batteries, amorphous Si performs better. Lithium insertion is generally assumed to be a disordering process, and a mesostable glass is obtained. As a result, some noncrystalline materials such as nonmetals and metals can be added to get amorphous Si. Its reaction with Li is shown as follows ... 

The terminal alloy is Li22M5, with a theoretical capacity of about 1600 mAh/g. Compared with Si-based materials, Ge exhibits a higher diffusivity for lithium ions (about 400 times greater than that in silicon at room temperature) and a lower specific volume change during the Li insertion/extraction process, which is expected to present better cycling performance at comparable capacity, and therefore shows promise as a negative electrode material for lithium-ion batteries. 

Relatively high lithium ion conductivity was observed in perovskite-type SrV03 in which lithium ions were electrochemically inserted [50]. This material is an electronic conductor and has been studied as a candidate for a high-performance cathode material for lithium ion batteries. The lithium ion conductivity in this oxide is estimated to be about 10 S cm at room temperature. 

The work presented in this chapter involves the study of high capacity carbonaceous materials as anodes for lithium-ion battery applications. There are hundreds and thousands of carbonaceous materials commercially available. Lithium can be inserted reversibly within most of these carbons. In order to prepare high capacity carbons for hthium-ion batteries, one has to understand the physics and chemistry of this insertion. Good understanding will ultimately lead to carbonaceous materials with higher capacity and better performance. 

The Li-Ion system was developed to eliminate problems of lithium metal deposition. On charge, lithium metal electrodes deposit moss-like or dendrite-like metallic lithium on the surface of the metal anode. Once such metallic lithium is deposited, the battery is vulnerable to internal shorting, which may cause dangerous thermal run away. The use of carbonaceous material as the anode active material can completely prevent such dangerous phenomenon. Carbon materials can intercalate lithium into their structure (up to LiCe). The intercalation reaction is very reversible and the intercalated carbons have a potential about 50mV from the lithium metal potential. As a result, no lithium metal is found in the Li-Ion cell. The electrochemical reactions at the surface insert the lithium atoms formed at the electrode surface directly into the carbon anode matrix (Li insertion). There is no lithium metal, only lithium ions in the cell (this is the reason why Li-Ion batteries are named). Therefore, carbonaceous material is the key material for Li-Ion batteries. Carbonaceous anode materials are the key to their ever-increasing capacity. No other proposed anode material has proven to perform as well. The carbon materials have demonstrated lower initial irreversible capacities, higher cycle-ability and faster mobility of Li in the solid phase. 

Letellier M., Chevallier F., Clinard C., Frackowiak E., Rouzaud J.N., Beguin F. The first in situ 7Li nuclear magnetic resonance study of lithium insertion in hard-carbon anode materials for Li-ion batteries, J. Chem. Phys. 2003 118 6038-45... 

A wide variety of carbonaceous materials can intercalate or insert lithium reversibly and thus may be candidates for anodes for lithium ion batteries. In recent years, many types of carbons have been tested as alternative anodes for rechargeable lithium batteries, part of which have found use as anodes in practical, commercial lithium ion batteries. The most straightforward way of classifying these electrodes is according to the type of the carbon, which determines their capacity and basic electrochemical behavior. The major types of carbons tested in recent years as anode materials for Li ion batteries are listed below ... 

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