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The Project BIELECTRONIC ACCUMULATOR Nanotechnologies for Durable, Long-Life Supercompact Electric Accumulator Batteries A novel technology is suggested for creating bielektronic accumulators - electric accumulator batteries on the basis of capacitors made of a nano-structured dielectric - to obtain a specific capacity of 1.6 MJ/kg, with no limits to the recharge cycle number. The operating temperature range would be from - 70°C to +300°C, with the continuous operation lifetime extended to no less than 30 thousand hours. 1. Problems Related to Mobile Sources of Electric Energy Accumulator batteries are reusable chemical sources of electric energy (power). Every of them consists of two electrode plates (anode and cathode), electrolytic solution and a jar. Energy storage in an accumulator battery is provided by the chemical oxidoreduction reaction of the electrode plates. The inverse processes occur with discharge of an accumulator battery. Accumulator voltage is a potential difference between the poles of an accumulator battery with a certain fixed load. Accumulators were invented the middle of 19th century. Until now, they have been subject to constant technologic development. However, no qualitative leaps have ever occurred in production of storage batteries, in contrast to the electronic engineering field, with its sweeping transition from high-vacuum tubes to transistors and integrated circuits. Accumulators differ both in their design and in the type of the physical chemistry processes utilized. The most widely used are hermetically sealed lead-acid (SLAs), nickelcadmium (NiCd), nickel-metal-hydride (NiMH), lithium ion (Li-Ion) and lithium-polymer (Li Polymer) storage batteries. Conventional modern lead batteries have the specific capacity of 0.08 MJ/kg, nickel accumulator batteries - 0.2 MJ/kg, sodium-sulfur storage batteries - 0.4 to 0.6 MJ/kg at operating temperatures over 500°K and Li-Polymer storage batteries - 0.6 to 0.7 MJ/kg at room temperature. The most advanced lithium accumulator batteries for cell phones are known to have been developed by the Kokam Engineering Company in South Korea (http://www.kokam.co.kr/english/product/battery01.html). Present-day accumulator batteries are used for limited numbers of recharge cycles (ranging from 200 to 1000), which sets limits to the operation lifetime of such batteries at 1.5 to 2 years. With that, they are environmentally unsafe and heavy maintenance burden. Table 1. Some characteristics of accumulator batteries (according to Batteries in a Portable World by Isidor Buchmann; http://www.terralab.ru/supply/7853/) [Feature] Description/ Type of Chemistry NiCd SLA NiMH Li-Ion Li-Polymer 1 2 3 4 5 6 Low low high medium medium 1500+ 200 to 500 500 500 – 1000/ 1.5 years 100 - 150/ 1.5 years less than 1.5 8 - 16 2- 4 3- 4 8 - 15 High low low medium medium 40 – 60 30 60 - 80 100 150 - 200 Impendance Number of ‘charge-discharge’ cycles /operation lifetime (times/years) Charging time (hours) Current drain profile Power density, Wh/kg Total monthly self-discharge share (per cent) Maintenance required to keep up the capacity 1 20 Monthly 5 30 10 10 once in 3 - once in 2 not required not required 6 months 3 months 2 3 4 5 6 Cost of a ‘charge - discharge’ cycle for the cells used in mobile devices consuming 6 – 9 V (USD) 0,04 0,1 0,14 0,2 0,6 Market entry record 1950 1970 1990 1991 2000 A battery for storage of electric energy is the integral part of any power-generating system, as it helps smoothing away peak loads. It would be impossible to provide a constant power supply of premises from solar photovoltaic cells without such batteries, nor to create electric vehicles or hybrid vehicles, etc. Furthermore, if, an accumulator meant for use in vehicles should have high profiles of specific capacity and number of recharge cycles, along with good charging/discharging dynamics. Vehicle accumulators are designed to ensure operation of ignition systems in the starter mode and at starting internal combustion engines; they also serve as the power source for the vehicle-born equipment. Usually their service life period spans for about 2 years, with the operating time 2500 to 3000 hours. They are designed for use at temperatures from –35°C to +60°C. Energy density of starter batteries amounts to about 0.1 MJ/kg. Regretfully, the problem of storage batteries for electric vehicles was not solved within the last hundred years. With the conventional batteries the maximums in power density achieved are at least one tenth of the required values. Furthermore, the transition to battery-driven vehicles will demand an enormous number of new power stations to be created. With the total losses through the entire cycle of electric power generation and charging of accumulator batteries, the overall efficiency will be brought to the utmost of 30 - 35%. Therefore nowadays the large-scale transition toward electric vehicles is regarded as a domain with no prospects for the energy-efficient future. However, battery-driven vehicles still remains an object of high environmental urgency in large cities. Thus, by 2009, the total of 2.5 million electric and hybrid vehicles are to be manufactured around the world. (http://www.freedoniagroup.com/WorldElectric-Vehicles.html). Besides, accumulator batteries will take a substantial share of the vehicle prices; more to that, the batteries must be changed every 2 years of the operation of the vehicles. The absence of compact, long-life yet cheap accumulator batteries urge the automotive corporations to boost their development of vehicles with environmentally safe engines, including those based on fuel elements (FEs). The fuel elements ensure direct transformation of chemical energy of a fuel into electricity, leaving out the ineffective combustion processes with the large losses of energy. These electrochemical devices generate electric energy being a direct output of the high-yield “cold” combustion of a fuel. Due to their high cost, FEs are mainly used in aerospace technologies. At present much effort is focused on the studies of FEs, for the commercial application thereof. Electricity in an FE is generated from direct low-temperature oxidation of fuel upon the catalysts at low temperatures, within the range of 300 - 500°K, the efficiency amounting to 80% (with oxidation of hydrogen gas). However, with the hydrocarbon fuels used, the FEs’ efficiency is cut to 40 - 45%. This has to do with the necessity of primarily cracking such fuels into their components to obtain hydrogen. The direct use of methane, spirit and the like reduces the efficiency even more. As a result, FEs’ intrinsic advantages, so attractive to power engineering, are lost. The area of application is narrowed down to the sector of the mobile 2 devices, where there are no strict requirements of high efficiency. Besides, all FEs provide low power density rates, which demands additional accumulator batteries for peak loads. Several companies, specialized in development of fuel cell systems for mobile electronic devices, have at the same time claimed this technology to be commercialized in the near future. Smart Fuel Cell AG (Germany), Casio, Toshiba and NEC (Japan) are among those companies. The FE share in their cell systems is not larger than 10 – 30%, while their energy density amounts to about 1 MJ/kg. Thus, the performance parameters of FEs are tenfold better than those of nickel-cadmium storage batteries. An FE does not require long recharging from electric mains, just replacement of a containers with a liquid organic fuel. However, because of the low specific current density, FEs are to be used with additional, bypass accumulators in vehicles or in cell phones. Consequently, we are back again, facing the problem of accumulator batteries. As appears from the above, of all chemical sources of current supply, fuel elements can be beaten only by the electric accumulator batteries of no less than 1 MJ/kg specific capacity, providing the unlimited number of cycles of short, almost instantaneous recharging. 2. Alternative Approach to Creation of Mobile Sources of Electric Power We rejected the standard pattern of creation of electrolytic accumulator batteries (wherein the charge is carried by heavy ions) and proceeded to storage of electron pairs in a nano-structured dielectric capacitor. The dielectric is structured in such a way that the electrons form evenly distributed pairs throughout the entire volume of the dielectric material. This made possible to increase the specific density of the stored energy several thousands times, in comparison with the feature of ceramic and chemical capacitors. Consequently, there can be devised a fundamentally new technology for creation of a storage battery on the basis of the nano-structured dielectric capacitor, to ensure a specific capacity of 1.6 MJ/kg at normal operating temperatures, along with virtually unlimited number of charging/discharging cycles – a bielektronic accumulator battery. The specific capacity of such batteries will be 2 - 3 times larger than that of the best lithium-polymer storage batteries, with the production costs not exceeding those of the lithium-polymer technology. The operating temperature span will be from -70ºC up to 300ºC. The period of continuous operation will be extended to about 10 - 30 years. Furthermore, the proposed type of accumulator batteries could completely replace all the types of disposable solid chemical battery power supplies (battery cells) and create the opportunities for enormous material savings. 2.1. Know-how. Brief Description We have made theoretical and experimental studies on creation of capacitors that would allow the maximum specific energy storage possible, low leakage current rates and high-speed profiles. Dielectric constants of the known dielectrics is ε ≤ 1000 and low strength E of the electric field, which does not allow to obtain high specific energy density values. There are two methods for increasing the energy density rates – either by providing higher ε, or by higher field strength E, which is more effective. However, increase in E causes irreversible dielectric breakdowns. The breakdowns in solid dielectrics occur due to the emission of electrons into the dielectric from the capacitor coatings. Having been emitted into the dielectric and exposed to the accelerating electric field, the electrons move from the cathode to the anode. On their way they collide repeatedly, which leads to formation of an electron avalanche, i.e. the breakdown. The collision ionization results in creation of positive ions that remain in the avalanche track and build up a remanent charge. Besides, an increase in thickness of dielectrics produces the socalled “bulk effect”, i.e., the dielectric breakdown voltage gets sharply down, which causes the decrease of the specific energy accumulated. The avalanche breakdown results in destruction of 3 the dielectric material and formation of an irrepairably defective channel. As an ultimate result of all this, the capacitor fails. At present there are many theoretic insights of the mechanism of dielectric breakdown. However, all of them offer solutions of just some particular problems by approximated methods. Certain amount of research has been made in this direction to study the new mechanism of energy storage in the entire volume of solid dielectrics, owing to control of breakdowns mechanism and restoration of the operating characteristics of the dielectric materials. A new mechanism of electron current in dielectrics and semiconductors was investigated for simultaneously increased ε and E, taking into account the three-dimensional wave structure of electron (as published in application PCT BY 99/00012). As a result of our studies, a new class of nano-structured materials of a super-large dielectric permeability (ε = 2·106) has been detected. Preliminary laboratory tests have revealed good results and proved practicability of designing accumulator batteries with fundamentally new consumer properties: • specific capacity - 1.6 MJ/kg, which is 16 - 20 times higher than that of lead batteries; • admissible deep discharge in the starter mode; • unlimited number of recharge cycles; • virtually instantaneous charging; • no requirements of operating maintenance; • unlimited service life and no limits to uncharged storage; • pollution-free production, operation, salvage and recycling. This would enable us of solving the problems related to solar power engineering, hybrid and battery vehicles, mobile electronics. 3. Markets for Accumulator Batteries The markets for accumulator batteries are remarkable for the exceptional variety of their segments: • mobile electronics (cell phones, video equipment, etc.); • substitutes for all the types of single-use solid chemical sources of power supply (batteries); • storage batteries for every transport means; • stationary by-pass accumulators for the solar, thermal and atomic power plants. Each year, till 2007, the global demand for disposable and rechargeable power cells will grow by 6,4%. The most rapidly growing markets will be in China, India, Brazil and South Korea; the USA, Western Europe and Japan are also likely to experience an up-going demand for them. Rechargeable non-lead batteries will outstrip the disposable cells and lead acid batteries. (http://www.freedoniagroup.com/World-Batteries.html). The world markets for production of storage batteries are estimated for as much as USD43 milliard. There are more than 30 leading manufacturers of storage batteries in the world, including Matsushita Electric Industrial, Exide, Duracell, Sanyo Electric, Energizer Holdings, Toshiba, Johnson Controls, and VARTA. Storage batteries for the vehicles with electric drives – i.e. hybrid and battery vehicles – take a special niche. The costs of such storage batteries make 10% to 30% of the total cost of the entire vehicles. By 2009 the sales of electric vehicles will reach 2.5 million pieces worldwide, their market estimated as much as USD 45 milliard. Their production growth will be caused by the problems of environment preservation, stimulated by production preferences or benefits and spurred by high oil prices. Hybrid vehicles and fuel cell vehicles will prevail; the market share of the transport means powered only from storage batteries will be subject to the declining tendency. (http://www.freedoniagroup.com/World-Electric-Vehicles.html). 4 The absence of the storage batteries with the necessary consumer properties is the restraint that keeps this market from growing today. More than 30 leading industrial companies, including DaimlerChrysler, Ford, General Motors, Honda and Toyota, have dwelled upon production of electric vehicles. Stationary bypass storage batteries are necessary to be used to increase the efficiency of renewable energy sources and power mini-plants. The global demand for power mini-plants (the so-called “micropower” units) will grow yearly by 13% till 2007, as by using such units the environmental impact can be reduced. The greatest production growth in the microturbine and fuel cell sectors will be observed in North America. Solar photo cells, wind electric generators and other renewable energy sources will enjoy the utmost development advance in Asia and Europe. The specialized world markets will reach the sale amount of USD16 milliard. (http://www.freedoniagroup.com/World-Micropower.html). Generally, costs of storage batteries for solar and wind power stations are commensurable with the cost of the power units. Production of mini power units is the domain shared most entirely by 25 key companies, including Caterpillar, Cummins, NEG Micon, Vestas, BP Solarex, Kyocera, ABB, Alstom, Mitsubishi Heavy Industries, and Siemens. As a summary of the above, the sales total of the promising world markets for storage batteries is likely to make about USD 60 milliard by 2009 (http://www.freedoniagroup.com/). The high level of patent protection of the production technologies of bielectronic accumulators provides the opportunity to monopolize the markets for such batteries for 15 - 20 years. Furthermore, mass production of the bielectronic storage batteries paves the way to creation of high-performance electric vehicles, solar power stations, etc. 4. Marketable Products of the Firm Limited licenses for production technology of bielectronic storage batteries meant for various segments of the Chinese and Belorussian markets for storage batteries of specific requested characteristics. Selection and instruction of the personnel for license buyers. Preparation of the "umbrella" of patents related to basic application PCT BY 99/00012 and Patent EA No.003852 for the production technology of the bielectronic accumulator, in order to protect the rights of the licenses buyers and build up the intangible assets of the JV. 5. Technical Feasibility and Marketability of Mass Production of Bielectronic Accumulator Batteries The production methods for nano-clusters and nano-tubes, both being the basic elements of bielectronic accumulators, allow creating nano-structured materials based on the available technologies. In the electrical engineering industry extensively used are dielectrics with a nonlinear characteristic. These materials provide the basis for making input voltages limiters (varistors). This production is well developed and set. It is simple a task to manufacture clusters of the necessary size that would evoke the resonance properties of electrons, whereby the material would acquire new properties of an energy accumulator. As regards the power engineering sector, a simpler technology for making nanostructured materials, based on nano-porous foam, could be used for the purpose of buffer accumulation of large amounts of energy. For this, it is necessary to finish the development of the carbonic foaming technologies or the synthesis of nano-porous silicate glass. The synthesis of spherical porous particles by the sol-gel method is also cheap enough. This method would provide us with the nano-structured material for the bielectronic accumulator. The materials used for the technology are well known and produced by the industry in sufficient amounts; they are ecologically clean and relatively inexpensive. 5 6. Risks In the case of obtaining bielectronic accumulators of tenfold less specific capacity than proclaimed, they would still remain competitive on the markets for vehicle accumulator batteries. Should their capacity be 3 - 5 times smaller than the proclaimed parameter, they would remain competitive in all the segments of the entire market for storage batteries. Professor Alexander M. Ilyanok 6