CR2032 button cell

In-depth study of the CR2032 button cell industry chain

Hydrogen is currently recognized as the cleanest fuel in the world and is also an important chemical synthesis raw material. Hydrogen is not a primary energy source. It needs to use primary energy to convert it to produce energy carriers. At present, most industrial applications of hydrogen use high-pressure gaseous forms as fuel or raw materials. Hydrogen CR2032 button cell vehicles (Fuelcellvehicle-FCEV) use hydrogen or hydrogen-containing substances and oxygen in the air through CR2032 button cells to generate electricity, and then use electricity to drive the motor, which drives the vehicle. The whole process converts the chemical energy of hydrogen into mechanical energy. The biggest benefit of hydrogen energy is that it reacts with oxygen in the air to produce water vapor and then discharges it, which can effectively reduce the air pollution caused by fuel vehicles. At this stage, high-speed vehicles, buses, submarines and rockets have used hydrogen fuel in different forms, and CR2032 button cell vehicles are generally improved on the basis of internal combustion engines.

The biggest obstacle that restricts hydrogen CR2032 button cells from truly becoming practical, market-oriented, and popular is the economic scale of hydrogen production, hydrogenation technology and its social prevalence, and the reliability of technology (fuel stack and vehicle technology). We have elaborated on the economic scale of hydrogen production in the CR2032 button cell industry in-depth report (I). This article, as the second in the series of reports, will focus on hydrogenation technology and its social prevalence, that is, the construction of hydrogenation stations and networks.

For economic scale hydrogen production, in the CR2032 button cell industry in-depth report (I), we analyzed the possible sources of low-cost hydrogen sources. We believe that from the current point of view, the utilization of domestic chemical by-product hydrogen is the best choice for hydrogen supply in the CR2032 button cell industry. The domestic chlor-alkali, PDH and rapidly developing ethane cracking industries can provide sufficient low-cost hydrogen resources, and they are concentrated in the East China region with dense load centers. After low-intensity transformation of these devices, the problems of hydrogen supply and efficient utilization of by-product hydrogen in the CR2032 button cell industry can be solved at the same time. In the future, centralized hydrogen supply from chemical by-products + decentralized hydrogen production by water electrolysis will be the development direction of the hydrogen supply model in the domestic CR2032 button cell industry.

As the second report in the series, in this article we will discuss the technical difficulties of hydrogenation station construction. According to different classification methods, hydrogenation stations can be divided into many types: according to the location of hydrogen production, hydrogenation stations can be divided into off-site hydrogenation stations (off-site) and on-site hydrogenation stations (on-site); according to the storage location, they can be divided into fixed hydrogenation stations and mobile hydrogenation stations; according to the hydrogen storage state, they can be divided into liquid hydrogenation stations and high-pressure hydrogenation stations; according to the filling method, they can be divided into single-stage filling stations and multi-stage filling stations; according to the hydrogen production method, hydrogenation stations can be divided into water electrolysis hydrogenation stations, industrial by-product hydrogenation stations, natural gas reforming hydrogenation stations, methanol reforming hydrogenation stations, etc.

The industry usually divides hydrogenation stations into off-site hydrogenation stations and on-site hydrogenation stations. There is no hydrogen production device in the off-site hydrogenation station. Hydrogen is transported from the hydrogen source to the hydrogenation station. After the hydrogen is transported to the hydrogenation station, it is compressed, stored, and refilled in the station. The on-site hydrogenation station has its own hydrogen production system in the hydrogenation station, which can independently produce hydrogen. The hydrogen is purified and compressed before storage. At present, small on-site hydrogenation stations mainly use the method of on-site water electrolysis to produce hydrogen. In addition, there are also on-site natural gas reforming hydrogen production, methanol reforming hydrogen production, solar or wind energy hydrogen production, etc.

The hydrogen of the off-site hydrogenation station is transported from the hydrogen source to the hydrogenation station. The methods of hydrogen transportation include: gaseous hydrogen transportation, liquid hydrogen transportation, and solid hydrogen transportation. The former two pressurize or liquefy hydrogen and then use transportation tools to transport it. This is the more common method of hydrogenation stations at present. Solid hydrogen transportation is transported through metal hydrides.

2.1. Transportation of Gaseous Hydrogen (GH2)

The transportation of gaseous hydrogen usually involves pressurizing hydrogen to a certain pressure and then transporting it using containers, long-tube trailers, pipelines and other tools.

The container consists of multiple high-pressure hydrogen cylinders with a water volume of 40L, and the filling pressure is usually 15Mpa. The container is flexible in transportation, and it is an ideal transportation method for users with small demand.

The long-tube trailer consists of a head and a trailer. The tube bundle is used as a hydrogen storage container. The commonly used tube bundle is generally composed of 9 cylinders with a diameter of about 0.5m and a length of about 10m. The designed working pressure is 20Mpa, and it can store about 3500 standard m3 of hydrogen. The long-tube trailer technology is mature and the specifications are perfect. Therefore, many hydrogen refueling stations abroad use long-tube trailers to transport hydrogen, and Shanghai's large-scale commercial hydrogen uses this method. Shanghai Pujiang Special Gas Co., Ltd. is one of the earliest domestic enterprises in China to use long-tube trailers to transport hydrogen.

After the hydrogen long tube trailer transports hydrogen to the hydrogen filling station, the tube bundle containing hydrogen is separated from the tractor and then connected to the gas unloading column. The hydrogen then enters the compressor for compression and is successively sent to high-pressure, medium-pressure and low-pressure hydrogen storage tanks for graded storage. When the car needs to be refueled, the hydrogen filling machine can take gas from the hydrogen long tube trailer, low-pressure hydrogen storage tank, medium-pressure hydrogen storage tank and high-pressure hydrogen storage tank in sequence for refueling.

In the United States, Canada and Europe, there is a way to transport hydrogen by pipeline. The pipeline diameter is about 0.25~0.3m, the pressure range is 1~3MPa, and the flow rate is between 310~8900kg/h. At present, the total length of hydrogen pipelines has exceeded 16,000km. The investment cost of the pipeline is very high, which is related to the diameter and length of the pipeline. It is 50%~80% higher than the cost of natural gas pipelines. Most of the cost is used to find a suitable route. At present, hydrogen pipelines are mainly used to transport hydrogen in chemical plants.

2.2. Liquid hydrogen (LH2) transportation

The volume density of liquid hydrogen is 70.8kg/m3, and the volume energy density reaches 8.5MJ/L, which is 6.5 times that of gaseous hydrogen at a transportation pressure of 15MPa. Therefore, deep cooling hydrogen to 21K to liquefy it and then transporting it by tank truck or pipeline will greatly improve the transportation efficiency. The volume of a tank truck is about 65m3, and it can transport about 4000kg of hydrogen each time. Therefore, foreign hydrogen refueling stations use liquid hydrogen transportation more than gaseous hydrogen transportation. Liquid hydrogen pipelines are insulated with vacuum jackets, which consist of two concentric sleeves with equal cross-sections inside and outside, and a high vacuum is drawn between the two sleeves.

In addition to tank trucks and pipelines, liquid hydrogen can also be transported over long distances or across continents by rail and ship. Deep-cold railway tank trucks are a fast and economical way to transport liquid hydrogen over long distances, which can meet the needs of large hydrogen transport volumes. This type of railway tank car often uses a horizontally placed cylindrical Dewar tank, which can store liquid hydrogen up to 100m3. Special large-capacity railway tank cars can even transport 120~200m3 of liquid hydrogen. Currently, only a very small amount of hydrogen is transported by rail.

The liquid tank car transports liquid hydrogen to the hydrogen refueling station, and enters the liquid hydrogen storage tank of the hydrogen refueling station after connecting to the hydrogen refueling station. The hydrogen in the liquid hydrogen storage tank is gasified by the gasifier, and then enters the buffer tank, and then enters the compressor to be compressed, and is successively transported to the high-pressure, medium-pressure, and low-pressure hydrogen storage tanks for graded storage. When the car needs to be refueled, it can be refueled in sequence from the low-pressure, medium-pressure, and high-pressure hydrogen storage tanks.

2.3. Solid hydrogen (SH2) transportation

The transportation of solid hydrogen mainly utilizes the hydrogen absorption characteristics of metals or alloys such as rare earth, titanium, zirconium, and magnesium to react with hydrogen to produce stable hydrides, and then release hydrogen by heating after being transported to the destination at normal temperature and pressure. There are four types of hydrogen storage alloys that are being studied more: rare earth lanthanum nickel, etc., which can store 135L of hydrogen per kilogram; iron-titanium series, which can store four times more hydrogen per kilogram than rare earth lanthanum nickel, and are low-priced, highly active, and can release hydrogen at room temperature and pressure, and are currently the most used hydrogen storage materials; magnesium series, which is the metal element with the largest hydrogen absorption capacity, but the release temperature needs to reach 287 degrees Celsius, and the hydrogen absorption speed is slow; vanadium, niobium, zirconium and other multi-element series, these metals themselves are rare and precious metals, so they are only suitable for special occasions.

Using this technology can greatly increase the volume energy density of hydrogen transportation. In theory, the amount of hydrogen that can be absorbed by a hydrogen storage alloy of the same weight as a high-pressure steel cylinder is thousands of times that of a high-pressure steel cylinder, but the hydrogen storage alloy itself is expensive, and it is not realistic to use it for large-scale hydrogen transportation.

2.4. Transportation cost analysis

There is no unified standard for the cost of hydrogen transportation. In the "Comparison of Hydrogen Transportation Schemes for Hydrogen Refueling Stations" published by Ma Jianxin et al., the costs of long-tube trailer transportation, liquid hydrogen tanker transportation, pipeline transportation and other transportation methods were analyzed by modeling. In the model, they fixed the transportation distance from the hydrogen source to the hydrogen refueling station as 50km, considered factors such as fixed equipment investment, labor, energy consumption and operation and maintenance costs, and finally concluded:

When the number of hydrogen refueling stations is more than 8, the transportation cost of long-tube trailers is stable at 2.3 yuan/kg, equivalent to 46 yuan/(ton·km). If the number of hydrogen refueling stations is less than 8 and the scale is small, the utilization rate of long-tube trailers is low, which will increase the unit cost. The highest unit transportation cost is 4.7 yuan/kg, Equivalent to 94 yuan/(ton·km);

The transportation cost of liquid hydrogen tank trucks is the lowest. With the increase in the number and scale of hydrogen refueling stations, the lowest can be 0.4 yuan/kg, which is equivalent to 8 yuan/(ton·km). However, the cost of hydrogen liquefaction and evaporation is not taken into account. The investment in hydrogen liquefaction equipment is very huge. The investment in a liquefaction plant with a daily processing capacity of 120t of hydrogen is about 90 million US dollars. The liquefaction cost of a liquefaction plant with a liquefaction capacity of 30t per hour is 4.5 yuan/kg. Therefore, if the liquefaction cost is taken into account, the cost of transporting hydrogen by long-tube trailer is still relatively low at present;

The cost of transporting hydrogen by pipeline is mainly related to the transportation volume (the scale of hydrogen refueling stations). When the transportation volume reaches more than 1500kg/day, the transportation cost of hydrogen is 120 yuan/(ton·km).

In the above cost analysis, the transportation distance is fixed at 50km. In fact, the transportation cost is also closely related to the transportation distance. Jiuniu Research Institute analyzed the relationship between distance and freight and found that the cost per kilometer of liquid hydrogen tanker transportation decreases rapidly with the increase of distance. This is because the longer the transportation distance, the lower the amortized liquefaction cost per kilometer. When the transportation distance exceeds 300km, liquid hydrogen tanker transportation becomes more economical than long-tube trailer transportation.

In order for the car to carry enough hydrogen, the hydrogen must be compressed. The higher the compression pressure, the more hydrogen the tank can store and the greater its energy density. Therefore, the hydrogen storage tank pressure on CR2032 button cell electric vehicles in the world generally reaches 35MPa working pressure, and even 70MPa working pressure. As a hydrogenation station for hydrogenating cars, the pressure of hydrogen stored in its tank must be higher than the pressure of the car's hydrogen storage tank to ensure that the car is filled. Therefore, to truly fill CR2032 button cell electric vehicles and hydrogen internal combustion engine vehicles with hydrogen and use hydrogen as energy, the key lies in hydrogen boosting technology, storage technology and filling technology and its system integration, especially storage technology, which is the technical difficulty of hydrogen refueling stations. For in-station hydrogen production and hydrogenation stations, the technical difficulties also include hydrogen production technology and system integration.

Hydrogen refueling stations are similar to existing more mature compressed natural gas (CNG) refueling stations, mainly including gas unloading columns (off-station hydrogen production and hydrogenation stations), compressors, hydrogen storage tanks, hydrogenation machines, pipelines, control systems, nitrogen purge devices, venting devices and safety monitoring devices, etc. Whether it is an off-station hydrogen production and hydrogenation station or an in-station hydrogen production and hydrogenation station, its core equipment is the compressor, hydrogen storage tank and hydrogenation machine, which account for 30%, 11% and 13% of the construction cost of the hydrogenation station respectively. At present, the core equipment of domestic hydrogenation stations basically relies on imports.

1. Compressor

The compressor is the core device for pressurizing the hydrogen source and injecting it into the gas storage system. The output pressure and gas sealing performance are its most important performance indicators. At present, the compressors used in hydrogen refueling stations are mainly diaphragm compressors and ion compressors. Diaphragm compressors do not require lubricating oil, so they can obtain high-pressure hydrogen that meets the purity requirements of CR2032 button cell vehicles, and the output pressure limit of diaphragm compressors can exceed 100MPa, which is enough to meet the pressure requirements of hydrogen refueling stations above 70MPa, but diaphragm compressors need to be cooled by air cooling or liquid cooling during the compression process. At present, the main international manufacturers of diaphragm compressors are Hydro-PAC and PDC in the United States. The domestic special 718 institute can use the parts provided by PDC to complete the assembly. The Shanghai World Expo Hydrogen Refueling Station and Beijing Hydrogen Refueling Station are both imported products of PDC in the United States.

Ion compressors can achieve isothermal compression, but because the technology is not yet mature, they are not used on a large scale. 2. Hydrogen storage tanks

Hydrogen storage tanks largely determine the hydrogen supply capacity of hydrogen refueling stations. Hydrogen storage tanks in hydrogen refueling stations usually use three levels of pressure for storage: low pressure (20~30MPa), medium pressure (30~40MPa), and high pressure (40~75MPa). Sometimes hydrogen long tube trailers are also used as primary gas storage facilities (10~20MPa), forming a 4-level gas storage method.

Compared with high-pressure and high-temperature hydrogen containers such as petroleum hydrogenation reactors and coal hydrogenation reactors and traditional hydrogen bottle containers, hydrogen storage tanks at hydrogen refueling stations have the following 4 basic characteristics:

High pressure and room temperature and high purity of hydrogen, with the risk of hydrogen embrittlement in high-pressure hydrogen environment. The design pressure of 35MPa hydrogen storage containers at hydrogen refueling stations is generally 45, 47, and 50MPa; the design pressure of 70MPa hydrogen storage containers at hydrogen refueling stations is usually 82, 87.5, 98, and 103MPa. Under normal working conditions, the metal temperature of the hydrogen storage container shell mainly depends on the atmospheric environment temperature. In order to meet the high purity requirements of hydrogen for hydrogen CR2032 button cell vehicles, the purity of hydrogen in the hydrogen storage container is above 99.999%. Working in a high-pressure and room-temperature hydrogen environment for a long time, the hydrogen storage container material may produce high-pressure hydrogen environment hydrogen embrittlement, resulting in plastic loss, accelerated fatigue crack growth rate and decreased durability, which seriously threatens the safe use of hydrogen storage containers.

The pressure fluctuates frequently and over a wide range, which poses a risk of low-cycle fatigue damage (especially for commercial stations). At present, the pressure fluctuations of hydrogen storage tanks for hydrogen refueling stations are usually 103~105 times within the design life, which belongs to the category of low-cycle fatigue. Among them, the pressure fluctuations of hydrogen storage tanks for mobile (demonstration) stations are relatively few, while those for fixed (commercial) stations are relatively large. In addition, the pressure fluctuation range of hydrogen storage tanks for stations is relatively large, usually 20%~80% of the design pressure (or the corresponding nominal working pressure of the gas cylinder). Therefore, the fatigue failure problem of hydrogen storage containers for hydrogen refueling stations is very prominent, and fatigue failure must be considered during design. Similar to hydrogen storage containers for hydrogen refueling stations, storage tanks for compressed natural gas refueling stations also store a large amount of flammable and explosive media, and the pressure also fluctuates, but the pressure fluctuation range is small, and the fatigue failure problem is not prominent.

Large volume, high compression energy, hydrogen is flammable and explosive, and the failure hazard is serious. According to GB50516-2010 "Technical Specifications for Hydrogen Refueling Stations", the maximum hydrogen storage capacity of the first, second and third level hydrogen refueling stations is 8000, 4000 and 1000 kg respectively. For the third level station, based on the storage pressure of 45MPa and the temperature of 20°C, the volume of the hydrogen storage container is about 35m3, which means that at least 39 900L high-pressure containers are required. The physical explosion energy of each container is equivalent to 18.4kgTNT explosives. Once an explosion occurs, the shock wave, fragments and high temperature will cause serious damage.

For the public, involving public safety. Hydrogen refueling stations (especially hydrogen refueling stations in urban built-up areas)

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