Recent development of carbon materials for Li ion batteries

doi:10.1016/S0008-6223(99)00141-4

Carbon

Volume 38, Issue 2, 2000, Pages 183-197

https://doi.org/10.1016/S0008-6223(99)00141-4 Get rights and content

Abstract

Lithium ion secondary batteries are currently the best portable energy storage device for the consumer electronics market. The recent development of the lithium ion secondary batteries has been achieved by the use of selected carbon and graphite materials as an anode. The performance of lithium ion secondary batteries, such as the charge/discharge capacity, voltage profile and cyclic stability, depend strongly on the microstructure of the anode materials made of carbon and graphite. Due to the contribution of the carbon materials used in the anode in last five years, the capacity of the typical Li ion battery has been improved 1.7 times. However, there are still active investigations to identify the key parameters of carbons that provide the improved anode properties, as carbon and graphite materials have large varieties in the microstructure, texture, crystallinity and morphology, depending on their preparation processes and precursor materials, as well as various forms such as powder, fibers and spherule. In the present article, we describe the correlation between the microstructural parameters and electrochemical properties of conventional and novel types of carbon materials for Li ion batteries, namely, graphitizable carbons such as milled mesophase pitch-based carbon fibers, polyparaphenylene-based carbon heat-treated at low temperatures and boron-doped graphitized materials, by connecting with the market demand and the trends in Li ion secondary batteries. The basic scientific theory can contribute to further developments of the Li ion batteries such as polymer batteries for consumer electronics, multimedia technology and future hybrid and electric vehicles.

Introduction

Among the metals, lithium has great promise as an electrode material of batteries that can combine the lightest weight with high voltage and high energy density. Because lithium possesses the lowest electronegativity of the standard cell potential −3.045 V in the existing metals, it is the anode material that donates electrons the most easily to form positive ions [1]. However, the negative electrode of lithium metal has serious problems as secondary battery use, since it does not have a long enough cyclic life and there are safety aspects that need to be considered due to the dendrite formation on the surface of lithium metal electrode during charge/discharge cycles. In order to solve these problems a “locking-chair” concept has been established, in which the intercalation phenomena has been used as an anode reaction for lithium ion secondary batteries [2], [3], [4], [5]. The intercalation compound of lithium metal into graphite by vapor transport was first synthesized by Herold [6] as a graphite intercalation compound (GIC) with stage structure. Since then, extensive study has been performed to investigate the staging structure and charge transfer phenomena of the Li-GIC compounds, which have the composition of Li_xC₆, where 0⩽x⩽1, and x=3 under high pressure, into order and disordered host materials [7], [8], [9], [10], [11], [12].

In the rechargeable lithium ion batteries based on the “rocking chair” or “shuttle cock” concepts, the lithium ions intercalates have to shift back and forth easily between the intercalation hosts of the cathode and anode. Thus, the lithium ion secondary battery mainly consists of a carbonaceous anode and a lithium transition metal oxide such as LiCoO₂, LiNiO₂ and LiMn₂O₄ as the cathode, as demonstrated in Fig. 1a. The anode on Cu foil and the cathode on Al foil are formed into spiral or plate folded shapes that give the US18650 cylindrical type (18 mm φ and 650 mm high, Fig. 1b) and rectangular cells, respectively. Between these two electrodes is placed a porous polymer separator of polyolefin of about 25 μm thickness, made by polyethylene (PE) and polypropylene (PP) (Fig. 1b) [13], [14]. Fig. 2 shows the SEM photograph of the anode, in which carbon sheets are formed on both side of the Cu foil lead. The electrolyte is an organic liquid such as PC, EC+DEC or a recently developed gel-type polymer, which is stable under high voltages. In the electrolyte lithium salt such as LiClO₄, LiBF₄ and LiPF₆ is dissolved.

The theoretical lithium storage capacity of a graphite anode for a Li ion secondary battery has been considered to be 372 mAh/g, corresponding to the first stage LiC₆-GIC. The charge/discharge total reactions and the anode reaction based on Li⁺ intercalation and deintercalation are shown as follows [15]: $LiCoO_{2} + y C ⇄ Discharge Charge Li_{1−x} CoO_{2} +Li_{x} Cy$ $y C+ x Li+ x e^{−} ⇄ Discharge Charge Li_{x} C_{y}$

On the other hand, disordered carbons with Li storage capacity exceeding the theoretical capacity have been reported. This phenomenon is still difficult to explain by the above-mentioned GIC science, and new schemes needed to be established.

Various types of carbonaceous materials have been investigated experimentally and theoretically as the potential anode materials ranging from highly ordered graphites to disordered carbons. Investigations have focused on improving the specific capacity, cyclic efficiency and the cyclic lifetime of the energy storage devices. For the anode material of the lithium ion batteries the microstructure and morphologies must be controlled for practical devices. It has been well known that the performances of lithium ion batteries depend strongly on the thermal history and morphology of carbon and graphite materials used for the anode [16]. Much more effort has been paid to the identification the key parameters of the carbon and graphite materials used for the battery. Because carbon and graphite materials have large variety in their microstructure, texture, crystallinity and morphology, it has been important to design and choose the anode material from a wide variety in order to get better battery performances [17], [18], [19]. Two typical types of carbon materials, highly-ordered graphite heat-treated at high temperatures such as 3000°C and non-graphitizable carbon heat-treated at low temperatures such as 1100°C, have been used in the anode in commercial batteries. The precursor materials include cokes, polymers, fibers and many others. Also, the insertion behavior and the mechanism of the lithium ions into various kinds of carbon and graphite hosts have been extensively studied both experimentally and theoretically [20], [21], [22], [23], [24], [25]. In particular, the lithium insertion mechanism and electrochemical properties in low temperature carbons, unlike the case of well-ordered graphite, are not yet fully understood as described before, and the perfect analysis is indispensable for practical use. The low temperature forms of carbon might be very promising for the following stage of Li ion battery because of their superior capacity. Also, the low temperature forms of carbon would be preferable in order to decrease the amount of electrical energy used in anode production, since graphite materials for anode application are heat-treated at around 3000°C and about 200 ton/month are consumed.

In the present review, we discuss the recent achievements of carbon anode materials and their structural design for better performances of lithium ion batteries. In the past 6 years, since commercialization started, the discharge capacity of Li ion batteries has been improved 1.7 times, from 900 to 1500 mAh for a typical US 18650 type cell, and is expected to be as high as 1900 mAh/cell soon. This large improvement in capacity has been recognized mainly due to the contribution of carbon technology to the negative electrode. Further scientific, as well as technical, accumulation can develop an advanced Li ion battery, such as the polymer type thin card battery soon to be on the market, and also the technology can be used for future full electric vehicle (EV) applications.

Section snippets

Present status and future trends in Li ion battery market

Li ion secondary batteries are currently the best energy storage devices for portable consumer electronics, in comparison with other conventional batteries, because of the high energy density as shown in Fig. 3. They were first developed and commercialized by Sony in 1990 and have been used in a wide range of portable stationary such as notebook computers, cellular phones and digital video cameras, etc. [26]. As seen in Fig. 3, basically, lithium ion secondary batteries have the advantage of

Voltage profiles of carbon electrodes

In the electrochemical cell used in the present article, the electrodes of carbon materials are positive electrodes since the counter electrode is lithium metal, therefore lithium intercalation to carbon corresponds to the discharge process, whereas the deintercalation of lithium ions is a charge process.

Fig. 6 shows the voltage profiles for lithium/carbon electrochemical cells made from representative carbon and graphite materials [21]. The graphite electrode cell gives a reversible capacity

Effect of microstructure of carbon anode on the capacity

Fig. 9 shows the second cycle charge capacity as a function of crystal thickness, Lc₀₀₂, on various carbon fiber and PPP (polyparaphenylene)-based carbon electrodes [16]. Well-ordered graphites (Lc₀₀₂>20 nm) and low crystalline materials (Lc₀₀₂<3 nm) have a larger capacity. However, intermediate crystallite sizes (∼10 nm) possess minimum capacity. Dahn et al. [21] reported the same kind of dependency on charge capacity as a function of heat treatment temperatures. Of particular interest in

Effect of morphologies, carbon fibers for Li ion battery

Carbon fibers used for electrodes in lithium ion batteries are roughly classified into two types such as milled mesophase pitch-based carbon fibers and gas phase grown carbon fiber commonly called as vapor grown carbon fibers (VGCFs) [35]. The former is contributing as one of the practical and promising anode material with high density of electrode, larger discharge capacity and better output current performances. The latter can serve as conductive filler in anode and cathode electrodes. On the

The factors restricting the capacity and effect of heteroatom-doped carbons

As the structural factors affecting the anode characteristics of graphite, especially the capacity less than the theoretical value of 372 mAh/g, the effects of the a–b axis crystallite size [45], stacking fidelity [21], [46] and defect of the basal planes [44] have been proposed. Tatumi et al. [46] divided the discharge curve of graphitized MCMB at the threshold potential of 0.25 V, and evaluated the corresponding charge capacity as functions of graphitization degree and turbostratic components

Polymer battery

The name of “polymer battery”is defined like the battery which has a polymer electrode and/or electrolyte. Very recently, a Li ion battery with gel type polymer electrolyte has been commercialized which is only 3.6 mm thick, weighs 15 g and has a capacity of 500 mAh, as shown in the Table 1[56]. The gel electrolyte consists of poly(ethylene oxide) (PEO), poly(acrylonitrile) (PAN), and poly(vinylidene fluoride) (PVdF) as the host polymer, EC/PC as the plasticizer and LiPF₆ as the electrolyte

Conclusions and prospects

It is not an overstatement that the success of the Li ion batteries has been contributed to by the advancements in GIC and carbon sciences made before to the early 1990s. They had been able to provide newly designed anode materials for the batteries. Enhancement of the battery performances and cost reduction have been also achieved in past 7 years, and now further improvements in performances of the battery is necessary for future development. On the low temperature carbons with high

Acknowledgements

This research was partially supported by the Ministry of Education, Science Sports and Culture, Grant-Aid for Scientific Research on Priority Area (Carbon Alloys), No. 09243105. The author (M.E) wishes to thank Prof. M. S. Dresselhaus of MIT for helpful suggestion and discussion.

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Recent development of carbon materials for Li ion batteries

Abstract

Introduction

Section snippets

Present status and future trends in Li ion battery market

Voltage profiles of carbon electrodes

Effect of microstructure of carbon anode on the capacity

Effect of morphologies, carbon fibers for Li ion battery

The factors restricting the capacity and effect of heteroatom-doped carbons

Polymer battery

Conclusions and prospects

Acknowledgements

J. Phys. Chem Solids

Carbon

Synthetic Metals

Carbon

Solid State Ionics

J. Power Sources

Carbon

Electrochimica Acta

Carbon

Carbon

Carbon

J. Electrochem. Soc.

J. Electrochem. Soc.

J. Electrochem. Soc.

Bull. Soc. Chim. France

Nature

Sci. Ser.

Phy. Rev.

Adv. in Phys.

SSSR

High Pressure Research

New ceramics

J. Electrochem. Soc.