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

Manganese oxides for lithium batteries

Electrochromic tungsten oxide films: Review of progress 1993–1998

Graphene-based materials are gaining heightened attention as novel materials for environmental applications The unique physicochemical properties of graphene, notably its exceptionally high surface area, electron mobility, thermal conductivity, and mechanical strength, can lead to novel or improved technologies to address the pressing global environmental challenges This critical review assesses the recent developments in the use of graphene-based materials as sorbent or photocatalytic materials for environmental decontamination, as building blocks for next generation water treatment and desalination membranes, and as electrode materials for contaminant monitoring or removal The most promising areas of research are highlighted, with a discussion of the main challenges that we need to overcome in order to fully realize the exceptional properties of graphene in environmental applications

Environmental applications of graphene-based nanomaterials.

Recent advances to develop manganese-rich electrodes derived from ‘composite’ structures in which a Li2MnO3
				(layered) component is structurally integrated with either a layered LiMO2 component or a spinel LiM2O4 component, in which M is predominantly Mn and Ni, are reviewed. The electrodes, which can be represented in two-component notation as xLi2MnO3·(1 −
				x)LiMO2 and xLi2MnO3·(1 −
				x)LiM2O4, are activated by lithia (Li2O) and/or lithium removal from the Li2MnO3, LiMO2 and LiM2O4 components. The electrodes provide an initial capacity >250 mAh g−1 when discharged between 5 and 2.0 V vs. Li0 and a rechargeable capacity up to 250 mAh g−1 over the same potential window. Electrochemical charge and discharge reactions are followed on compositional phase diagrams. The data bode well for the development and exploitation of high capacity electrodes for the next generation of lithium-ion batteries.

Advances in manganese-oxide ‘composite’ electrodes for lithium-ion batteries

We report here the direct synthesis of a hexagonal form of manganese dioxide using mild hydrothermal methods. The reaction of potassium or sodium permanganate in water at 170 °C leads directly to potassium or sodium manganese dioxide, Alk≈0.25MnO2·0.6H2O, with a R3m rhombohedral structure like Lix(H2O)TiS2 and a 7 A repeat distance indicative of a monolayer of water between the manganese dioxide layers. This manganese oxide reacts readily and reversibly with lithium ions.

Hydrothermal Synthesis and Characterization of KxMnO2·yH2O

The hydrothermal synthesis of new oxide materials

Extensive research is currently underway to find promising candidates for cathode materials in lithium secondary batteries, and a manganese oxide that behaved like the layered LiCoCO{sub 2} would be a prime candidate for this application because of its high free-energy of reaction with lithium and relatively low cost. The reaction of potassium, sodium, and lithium permanganate in water at 170 C leads directly to potassium, sodium, and lithium manganese dioxides, A{sub y}MnO {center_dot} nH{sub 2}O, with a R{bar 3}m rhombohedral structure. These crystalline layered structures after dehydration readily and reversibly react with lithium through an intercalation mechanism. The capacity for lithium is a function of the alkali ion present, and the larger potassium ion maintains the capacity best. For lithium there is a tendency to convert to the spinel structure which leads to loss of capacity.

https://iopscience.iop.org/article/10.1149/1.1837554/pdf

Cathodic Behavior of Alkali Manganese Oxides from Permanganate

The hydrothermal synthesis of sodium manganese oxide and a lithium vanadium oxide

The hydrothermal reaction of manganese or vanadium oxides in the presence of organic cations leads to the formation of new layered structures. When nickel salts are hydrothermally reacted with tetramethylammonium permanganate a new orthorhombic form of nickel manganese oxide, NiMnO
 3
H
 x
 (where x≤1) is formed. It readily chemically intercalates lithium; it has space group Cmc2
 1
, a=2.861(1) A, b=14.650(1) A, and c=5.270(1) A. The magnetic properties of this compound are quite different from the ilmenite NiMnO
 3
 phase, showing paramagnetism above 390 K and more complex behavior below that temperature. The hydrothermal reaction of vanadium pentoxide with methylamine leads to a series of new layered vanadium oxides, which differ in structure from the corresponding ones prepared in the presence of the tetramethylammonium ion because of the existence of hydrogen bonding. Methylamine is the first organic to form a double sheet vanadium oxide, (CH
 3
NH
 3
)
 0.75
V
 4
O
 10
·0.67H
 2
O, with the δ-Ag
 x
 
V
 2
O
 5
 structure. (CH
 3
NH
 3
)
 0.75
V
 4
O
 10
·0.67H
 2
O is monoclinic, space group C2/m with a=11.673(1) A, b=3.668(1) A, c=11.095(1) A and β=99.865(5)°. (CH
 3
NH
 3
)V
 3
O
 7
 shows significant buckling of the layers compared with N(CH
 3
)
 4
V
 3
O
 7
, and has a monoclinic unit cell, space group P2
 1
/c with a=11.834(8) A, b=6.663(4) A, c=15.193(9) A and β=138.104(1)°.

https://physics.ohio-state.edu/~raju/files/pub-pdfs/pub-40.pdf

Rongji Chen

Papers

Hydrothermal Synthesis and Characterization of KxMnO2·yH2O

The hydrothermal synthesis of new oxide materials

Cathodic Behavior of Alkali Manganese Oxides from Permanganate

The hydrothermal synthesis of sodium manganese oxide and a lithium vanadium oxide

The hydrothermal synthesis of the new manganese and vanadium oxides, NiMnO3H, MAV3O7 and MA0.75V4O10·0.67H2O (MA=CH3NH3)