1:Research Status of PEMFC
The earliest research work of PEMFC in China was Changchun Institute of Applied Chemistry, which began to study PEMFC on 1990 with the support of China Academy of Sciences. Its work mainly focuses on the preparation process of catalyst and electrode and the development of methanol external reformer, and a prototype of 100WPEMFC has been manufactured. 1994 pioneered the research of direct methanol proton exchange membrane fuel cells. The Institute has established long-term cooperative relations with case western reserve university and Russian Institute of Hydrogen Energy and Plasma. Dalian Institute of Chemical Physics, Chinese Academy of Sciences carried out research on PEMFC in 1993, and did a lot of work in electrode technology and battery structure. At present, a single battery with working area of 140cm2 has been developed, and the output power reaches 0.35W/cm2.
Fudan University began to develop direct methanol PEMFC in the early 1990s, focusing on the preparation of polybenzimidazole membrane and electrode preparation technology. Xiamen University cooperated with Hong Kong University and CaseWesternReserve University in the United States to conduct research on direct methanol PEMFC.
From 65438 to 0994, Shanghai University cooperated with Beijing Petroleum University to study PEMFC (the key project of the Eighth Five-Year Plan), mainly studying the preparation technology of catalysts, electrodes and electrode membrane modules.
With the support of the Ministry of Ordnance Industry, Beijing Institute of Technology started the research of PEMFC in 1995, and the current density of single battery was 150mA/cm2.
The Institute of Engineering Thermophysics of Chinese Academy of Sciences began to study PEMFC from 1994, mainly using computational heat transfer and computational fluid dynamics to compare various schemes such as gas supply, humidification, heat removal and drainage, and put forward improved heat and mass transfer schemes.
Tianjin Electric Power Research Institute started the research of PEMFC in 1997, and plans to introduce 1.5kW battery from abroad, and carry out the research on the basis of analyzing and absorbing foreign advanced technology.
From 65438 to 0995, Beijing Fuyuan Company cooperated with Canadian New Energy Company to develop PEMFC, and a 5kW PEMFC prototype was successfully developed and accepted orders.
2. Introduction 2:MCFC research
There are not many units that carry out MCFC research in China. Harbin Power Supply Equipment Research Institute began to study MCFC in the late 1980s, and stopped this research in the early 1990s.
65438-0993, Dalian Institute of Chemistry, Chinese Academy of Sciences, with the support of Chinese Academy of Sciences, started the research of MCFC, prepared LiAlO2 micropowder, prepared the separator for MCFC by cold rolling method and tape casting method, and assembled the single battery. Its performance has reached the international level in the early 1980s.
At the beginning of 1990s, Changchun Institute of Applied Chemistry of Chinese Academy of Sciences also started the research of MCFC, and made great progress in the preparation method of LiAlO2 micropowder and the research of intermetallic compounds as anode materials of MCFC.
In the early 1990s, University of Science and Technology Beijing carried out research on MCFC with the support of the National Natural Science Foundation, mainly studying the interaction between electrode materials and electrolyte, and proposed to use intermetallic compounds as electrode materials to reduce their dissolution.
3.3: Introduction to SOFC research
Shanghai Institute of Silicate, China Academy of Sciences conducted the earliest research on SOFC. They started their research on SOFC in 197 1, mainly focusing on the research on electrode materials and electrolyte materials of SOFC. In 1980s, with the support of the National Natural Science Foundation of China, SOFC research was started. The structure of zirconia membrane materials, cathode and anode materials and single SOFC prepared by tape casting method was systematically studied, and the technology of preparing stable zirconia nano-powder and dense ceramics by wet chemical method was preliminarily mastered. 1989 With the support of Jilin Youth Science Fund, Jilin University began to study the assembly of SOFC electrolyte, anode and cathode materials into single cells, and passed the appraisal of Jilin Science and Technology Commission. 1995 was funded by the Jilin Provincial Planning Commission and the State Planning Commission by 4.5 million yuan. The electrode, electrolyte, sealing and connecting materials were studied successively. The open-circuit voltage of single cell reached 1. 18V, and the current density was 400mA/cm2. The battery pack with four single batteries in series can make the radio and recorder work normally.
199 1 year, the research of SOFC was carried out by the Institute of Chemical Metallurgy of China Academy of Sciences with the support of China Academy of Sciences. Based on the research of materials, tubular and flat cell batteries were made, with power density of 0.09 w/cm2 ~ 0. 12 w/cm2 and current density of 150 ma/cm2 ~ 180 ma. 1994, the institute imported 20W~30W stacked SOFC batteries from the Institute of Electrochemistry, Ural Branch, Russian Academy of Sciences, and the battery life reached1200h ... On the basis of analyzing the stacked structure in Russia, the tubular structure of Westinghouse in the United States and the plate structure of Siemens in Germany, they designed a new hexahedral structure, which absorbed the advantages of unsealed tubular structure.
1992 south China university of technology started the research of SOFC with the support of the national natural science foundation, Guangdong natural science foundation, Shantou university Li Ka-shing research fund and Guangdong Foshan fund. The assembled tubular cell directly uses methane as fuel, and the maximum output power is 4mW/cm2, and the current density is 17mA/cm2, with continuous operation of 65,438. Developed countries take the development of large-scale fuel cells as a key research project, and enterprises have also invested heavily in the research and development of fuel cell technology, which has achieved many important results, making fuel cells widely used in power generation and automobiles, replacing traditional generators and internal combustion engines. It is worth noting that this important new generation mode can greatly reduce air pollution and solve the problems of power supply and peak shaving in power grid. 2MW, 4.5MW, 1 10MW complete sets of fuel cell power generation equipment have been put into commercial production, and fuel cell power stations of various grades have been built in some developed countries. The development and innovation of fuel cells will be like the industrial revolution triggered by the technical breakthrough that internal combustion engines replaced manpower a hundred years ago, the computer revolution in which the invention and popularization of computers replaced the calculation, drawing and document processing of manpower, and the information revolution in which the development of network communication changed people's living habits. Fuel cells have the potential of high efficiency, no pollution, short construction period, easy maintenance and low cost, which will detonate the green revolution of new energy and environmental protection in 2 1 century. Nowadays, in North America, Japan and Europe, fuel cell power generation is rapidly entering the industrial scale application stage, and will become the fourth generation power generation mode after thermal power, hydropower and nuclear power in 2 1 century. The rapid development of fuel cell technology abroad must attract our attention, which has become a subject that the energy and power industries have to face up to.
Phosphoric acid fuel cell (PAFC)
Affected by the 1973 world oil crisis and the research and development of American PAFC, Japan decided to develop various types of fuel cells. As a large-scale energy-saving power generation technology, PAFC was developed by NEDO. Since 198 1 year, the research and development of 1000kW on-site PAFC power generation device has been carried out. 1986, a 200kW field power generation device was developed, which is suitable for PAFC power generation devices in remote areas or for commercial use. Fuji Electric Corporation is the largest supplier of PAFC batteries in Japan. By the end of 1992, the company had provided 17 sets of PAFC demonstration devices at home and abroad. 1In March, 1997, Fuji Electric completed the operation research of distributed 5MW equipment. As field equipment, 88 kinds of equipment such as 50kW, 100kW and 500kW have been put into use. The following table shows the operation of power generation equipment delivered by Fuji Electric Company. By 1998, some parts have exceeded the target life of 40,000 hours.
Since the second half of 1970s, Toshiba has serialized distributed power sources with 1 10MW generator and 200kW generator, focusing on the development of distributed fuel cells. 1 10MW generator is the largest fuel cell power generation equipment in the world. From 1989, it was built in Tokyo Electric Power Company's Wujing thermal power station. After the successful power generation in early March, after more than five years of on-site testing, until June 1965438, the cumulative running time exceeded 20,000 hours. In the field of small-scale field fuel cells, in 1990, Toshiba and American IFC established ONSI Company to commercialize field fuel cells, and then began to sell the field-type 200kW equipment "PC25" series to the whole world. PC25 series fuel cells were operated from 199 1 at the end of the year to1April 1998, and * * * sold to the whole world 174 units. Among them, the 1 machine installed in a company in the United States and the No.2 machine of Osaka Gas Company installed in Meitian Center in Osaka, Japan have exceeded 40,000 hours successively. In terms of the life and reliability of fuel cells, the cumulative running time of 40000h is the long-term goal of fuel cells. Toshiba ONSI has completed the development of the official commercial machine PC25C and put it on the market. As a pioneer of new energy in 2 1 century, PC25C won the Japan International Trade and Industry Award. Since the commercialization of fuel cells, the equipment has been evaluated as advanced, reliable and superior environmental protection equipment. Its manufacturing cost is 3000 USD/kW, while the cost of commercial PC25D equipment will be reduced to 1.500 USD/kW, the volume is reduced by 1/4 compared with PC25C, and the mass is only 14t. 200 1 China will welcome the first PC25C fuel cell power station, mainly funded by Japanese MITI(NEDO), which will be the first fuel cell power station in China.
Proton exchange membrane fuel cell (PEMFC)
Ballard, a famous Canadian company, is a global leader in PEMFC technology, and its application fields range from vehicles to fixed power stations. BallardGenerationSystem, a subsidiary of Ballard Generation System, is considered as a world leader in the research, development, production and marketization of zero-emission proton exchange membrane fuel cells. BallardGenerationSystem's original product is a 250kW fuel cell power station, and its basic component is Ballard fuel cell, which uses hydrogen (obtained from methanol, natural gas or oil) and oxygen (obtained from air) to generate electricity without combustion. Ballard is cooperating with many famous companies in the world to commercialize BallardFuelCell. BallardFuelCell has been used in fixed power plants: BallardGenerationSystem was established by BallardGenerationSystem, GPUInternationalInc, AlstomSA and EBARA Company * * * to develop fuel cell power plants below kW level. After five years' development, the first 250kW power plant was successfully generated in August 1997, and was delivered to the National Energy Company of India in September 1999. After careful testing and evaluation, the design performance was improved and the cost was reduced, which led to the birth of the second power plant, which was installed in Berlin with an output of 250kW and was also the first test in Europe. Soon, Ballard's third 250kW power plant was installed in Switzerland in September, 2000 for field test. Then, in June, 2000, through its partner EBARABallard, the fourth fuel cell power plant was installed in NTT Company of Japan, which opened the Asian market. Testing in different fields will greatly promote the commercialization of fuel cell power plants. The first early commercial power plant will end on May 38, 2006. The following picture shows Ballard fuel cell device installed in Cinergy, USA, which is being tested.
The picture shows the 250kW PEMFC fuel cell power station installed in Berlin:
In the United States, PlugPower is the largest proton exchange membrane fuel cell development company, and their goal is to develop and manufacture economical fuel cell systems suitable for residents and automobiles. 1997, the PlugPower module successfully converted gasoline into electric energy for the first time. PlugPower Company developed its patented product PlugPower7000, which is a distributed power supply system for residential buildings. 200 1 Commercial products were launched at the beginning of the year. The introduction of domestic fuel cells will challenge nuclear power plants and gas-fired power plants. In order to promote this product,1February 1999, PlugPower Company and GEMicroGen established a joint venture company, and the product was renamed GEHomeGen7000, and GEMicroGen Company was responsible for the global promotion. This product will provide 7kW continuous power. GE/Plug company claims that its price at the beginning of 200 1 is 1500 USD /kW. They predict that in five years, the price of mass-produced fuel cells will drop to $500/kW. Suppose there are 200,000 families, and each family is equipped with 7kW household fuel cell power generation equipment, and the total will be close to the capacity of nuclear power units. This decentralized power generation system can be used for peak power supply, and because of the decentralized system design, the stability of power is increased. Even if several of them fail, the whole power generation system can still operate normally. Under the impetus of Ballard, many automobile manufacturers participated in the development of fuel cell vehicles, such as Chrysler, Ford, General Motors, Honda, Nissan, Volkswagen and Volvo. Many of the fuel cells they use are produced by Ballard Company. At the same time, they also invested a lot of money to develop fuel cells. Chrysler injected 450 million Canadian dollars into Ballard Company to develop fuel cell vehicles, which greatly promoted the development of PEMFC. 1997, Toyota built a RAV4 sports car with methanol reformer, which was supplied with all 50kW energy by a 25kW fuel cell and auxiliary dry cells, with a top speed of 125km/h and a journey of 500km. These big car companies all have fuel cell development plans. Although the time for commercialization of fuel cell vehicles is not yet ripe, several companies have determined the timetable for starting mass production. Daimler-Benz announced that it will produce 40,000 fuel cell vehicles every year by 2004. Therefore, in the next decade, it is very likely to reach100000 fuel cell vehicles.
Molten carbonate fuel cell (MCFC)
In the early 1950s, molten carbonate fuel cell (MCFC) attracted worldwide attention because of its prospect as a large-scale civil power generation device. After that, MCFC developed rapidly, and the material, technology and structure of the battery were greatly improved, but the working life of the battery was not ideal. In 1980s, it has been regarded as the second generation fuel cell, and it has become the main research goal of realizing megawatt commercial fuel cell power station, and its development speed is accelerating day by day. The main developers of MCFC are concentrated in the United States, Japan and Western Europe. It is expected to be commercialized in 2002.
In 2000, the U.S. Department of Energy allocated 44.2 million dollars for the research of fixed fuel cell power plants, of which 2/3 was used for the development of MCFC and 1/3 was used for the development of SOFC. The development of MCFC technology in the United States has always been mainly undertaken by two major companies, ERC(EnergyResearchCorporation) (now FuelCellEnergyInc) and M-CPower Company. They built MCFC reactors in different ways. Both companies have entered the stage of live demonstration: ERC 1996 has tested a 2MW MCFC power station in Santa Clara, California, and is looking for a site to test the 3MW equipment. ERC's MCFC fuel cell is reformed without fuel gas in the cell, and there is no separate reformer. According to the test results, ERC redesigned the battery, changing the battery into a 250kW single battery stack instead of the original 125kW battery stack, so that the 3MW MCFC can be installed on the site of 0. 1 acre, which reduces the investment cost. It is estimated that ERC will provide 3MW equipment at a cost of $ 1200/kW. This is close to the equipment cost of a small gas turbine generator of $65,438+0,000/kW. However, the efficiency of small gas-fired power generation is only 30%, and there are problems of waste gas emission and noise. At the same time, American M-CPower Company has tested the 250kW device at the Naval Air Station in San Diego, California, and plans to test and improve the 75kW device at the same place. M-CPower Company is developing 500kW modules and plans to start production in 2002.
The study of MCFC in Japan began with the "Moonlight Project" of 198 1 year, and turned to focus after 199 1 year. The annual expenditure of fuel cells is12-1500 million USD, and the government adds 200 million USD to 1990. The power of the battery stack is 1kW at 1984 and 10kW at 1986. Japan studies both internal transformation and external transformation technology, and 30kW indirect internal transformation MCFC was put into trial operation in 199 1 year. 1992 50- 100kW trial run. 1994, two MCFC with 100kW and electrode area 1m2 were completed by Hitachi and Ishikawa Island respectively, and were reformed under pressure. In addition, the 1MW external reforming MCFC produced by Central Electric Power Company is being installed in Sichuan-Vietnam Thermal Power Plant. It is predicted that when natural gas is used as fuel, the thermoelectric efficiency will be more than 45% and the service life will be more than 5,000 hours ... The 30kW internal reforming MCFC developed by mitsubishi electric in cooperation with ERC Company of the United States has been in operation10,000 hours ... Sanyo has also developed the 30 kW internal reforming MCFC. Ishikawa Island Drilling and Grinding Heavy Industry has the largest area of MCFC fuel cell stack in the world, and its test life has reached13000 h. In order to promote the research and development of MCFC, Japan established the MCFC Research Institute in 1987, which is responsible for the research on the operation of fuel cell stack, peripheral equipment and system technology of power plant. Joined 14 troops and became the main force of Japanese R&D..
As early as 1989, Europe formulated the 1 Joule plan, with the goal of establishing a "second generation" power plant with less environmental pollution, decentralized installation and 200MW power, including MCFC, SOFC and PEMFC, and distributing the tasks to various countries. The research on MCFC is mainly carried out in the Netherlands, Italy, Germany, Denmark and Spain. The research on MCFC in the Netherlands began with 1986, and the 1kW class battery stack was developed in 1989. 10kW external conversion type and 1kW internal conversion type battery stacks were tested at 1992, and coal gasification and coal gasification were tested at 1995. Italy began to implement the MCFC national research plan in 1986, and developed a 50- 100kW battery stack in 1992+0994. Italy's Ansodo Company signed an agreement with IFC on MCFC technology, and has installed a set of automatic production equipment for single battery (area 1m2), with annual production capacity. In 1992, German MBB Company completed the research and development of 10kW external conversion technology. With the assistance of ERC, the manufacturing and operation tests of 100kW and 250kW batteries were carried out in 1992-1994. Now, MBB has the largest 280 kW battery pack in the world.
Data show that MCFC has unique advantages compared with other fuel cells:
A. the power generation efficiency is higher than PAFC；;
B, expensive platinum is not needed as a catalyst, and the manufacturing cost is low;
C. carbon monoxide can be used as fuel;
D. Since the working temperature of MCFC is 600- 1000℃, the exhausted gas can be used for heating or combined with a steam turbine to generate electricity. If cogeneration, the efficiency can be improved to 80%;
E. Comparing several power generation modes, when the load index is greater than 45%, the cost of MCFC power generation system is the lowest. Compared with PAFC, although the initial investment of MCFC is higher, the fuel cost of PAFC is much higher than that of MCFC. When the power generation system is small and medium-sized decentralized, the economy of MCFC is more prominent;
The structure of MCFC is simpler than that of PAFC.
Solid oxide fuel cell (SOFC)
SOFC consists of electrolyte powered by ceramics such as yttria-stabilized zirconia (YSZ) and fuel and air electrodes powered by porous materials. Oxygen in the air is oxidized at the air electrode/electrolyte interface, moves to the fuel electrode side in the electrolyte under the action of oxygen difference between air and fuel, and reacts with hydrogen or carbon monoxide at the fuel electrode electrolyte interface to generate water vapor or carbon dioxide and release electrons. Electrons pass through the external circuit and return to the air electrode again, and electricity is generated at this time.
The characteristics of SOFC are as follows:
Due to the high temperature operation (600- 1000℃), by setting the bottom cycle, efficient power generation with efficiency over 60% can be obtained.
Because oxygen ions move in the electrolyte, CO and coal gasification gas can also be used as fuels.
Because the material of the battery body is solid, there is no evaporation and flow of electrolyte. In addition, the fuel electrode and the air electrode will not be corroded. The operating temperature is high, and internal modification such as methane can be carried out.
Compared with other fuel cells, the power generation system is simple, and it can be expected to develop from small-capacity equipment to large-scale equipment, which has a wide range of uses.
In the field of fixed power stations, SOFC has obvious advantages over PEMFC. SOFC rarely needs to treat fuel. Internal reforming, internal thermal integration and internal manifold make the system design simpler, and SOFC, gas turbine and other equipment are also easy to carry out efficient cogeneration. The picture below shows the world's first SOFC and gas turbine hybrid power station developed by Siemens Westinghouse. It was installed in the University of California in May 2000, with a power of 220kW and a power generation efficiency of 58%. The power generation efficiency of SOFC/ gas turbine will reach 60-70% in the future.
SOFC, known as the third generation fuel cell, is under active research and development, and is one of the emerging new power generation methods. The United States is the first country to study SOFC in the world, and Westinghouse Electric Company of the United States has played a particularly important role in it, becoming the most authoritative institution for SOFC research. As early as 1962, Westinghouse electric company used methane as fuel to obtain current in SOFC test device, and pointed out that hydrocarbon fuel must complete two basic processes: catalytic conversion and electrochemical reaction in SOFC, which laid the foundation for the development of SOFC. In the following 10 year, the company cooperated with OCR to connect 400 small cylindrical ZrO _ 2-Cao electrolytes and trial-produce 100W batteries, but this form is not suitable for large power generation devices. After 1980s, in order to open up new energy sources and alleviate the energy crisis caused by the shortage of oil resources, SOFC research has developed vigorously. Westinghouse Electric Company applied electrochemical vapor deposition technology to the preparation of SOFC electrolyte and electrode film, which reduced the thickness of electrolyte layer to micron level and significantly improved the performance of the battery, thus turning a new page in the research of SOFC. In the middle and late 1980s, it began to study high-power SOFC batteries. 1986,400w tubular SOFC battery pack was successfully operated in Tennessee.
fuel battery
In addition, some other departments in the United States also have certain strength in SOFC. PPMF located in Pittsburgh is an important production base for the commercialization of SOFC technology. With complete sets of equipment for SOFC battery component processing, battery assembly and battery quality inspection, it is the largest SOFC technology research and development center in the world. 1990, the center manufactured a 20kW SOFC device for DOE in the United States, which used pipeline gas as fuel and has been running continuously for more than 1700 hours. At the same time, the center also provided two sets of 25kW SOFC test devices for Tokyo Osaka Gas Company and Kansai Electric Power Company, one of which is a cogeneration device. In addition, argon National Laboratory of the United States also researched and developed SOFC stack with laminated corrugated plates, and developed casting method and calendering method suitable for the molding of this structural material. The energy density of the battery is significantly improved, which is a promising SOFC structure. In Japan, SOFC research is a part of "Moonlight Project". As early as 1972, the Institute of Electronic Integrated Technology began to study SOFC technology, and later joined the research and development ranks of "Moonlight Project". 1986 developed a 500W round tube SOFC battery pack, forming a 1.2kW power generation device. Tokyo Electric Power Company and Mitsubishi Heavy Industries started to develop the round tube SOFC device from 1986 to 65438+February, and obtained a single battery with an output power of 35 W. When the current density is 200mA/cm2, the battery voltage is 0.78V, and the fuel utilization rate reaches 58%. 1In July, 1987, the electric power development company cooperated with these two companies to develop the 1kW SOFC battery pack, with continuous trial operation of 1000h and maximum output of1.3kW. Kansai Electric Power Company, Tokyo Gas Company, Osaka Gas Company and other institutions imported 3kw and 2.5kW tubular SOFs from Westinghouse Electric Company. Since 1989, Tokyo Gas Company has also begun to develop large-area flat SOFC devices. 1June 1992, the flat SOFC device of 100W was completed, and the effective area of the battery reached 400cm2. At present, the power of flat SOFC developed by Fuji and Sanyo has reached kilowatt level. In addition, Central Electric Power Company cooperated with Mitsubishi Heavy Industries to study and comprehensively evaluate the SOFC system with laminated corrugated plates from 1990, and developed a 406W test device. The effective area of a single battery of the device reaches 13 1cm2.
In Europe, as early as the 1970s, the Academia Sinica in Heidelberg, the Federal Republic of Germany, developed a SOFC power generation device with a circular or semi-circular tube electrolyte structure, and the single battery operated well. In the late 1980s, under the influence of the United States and Japan, Europe actively promoted the commercialization of SOFC in Europe. Siemens, DomierGmbH and ABB research companies in Germany are committed to developing kilowatt-class flat SOFC power generation devices. Siemens also cooperated with the Netherlands Energy Center (ECN) to develop an open-plate SOFC battery with an effective electrode area of 67cm2. ABB Research Company has developed an improved flat kilowatt SOFC power generation device in 1993. The battery is a metal bipolar structure, and the experiment is carried out at 800℃, and the effect is good. Now we are considering making it into a 25 ~ 100 kW SOFC power generation system for domestic or commercial use.