Shulou(Shulou.com)11/24 Report--

Original title: "membrane method of hydrogen"

A global hydrogen arms race has begun.

With the rapid development and consumption demand of renewable energy such as wind and photovoltaics, coupled with the new energy security demand caused by regional conflicts, hydrogen energy has become the energy carrier that countries all over the world pay close attention to.

In this paper, we will directly cut into the specific technical route of the electrolytic cell, which is the key equipment for hydrogen production, and then further focus on one of the most important core components-the diaphragm and its development trend.

Chen Qianlei, author

Li Tuo (Editor)

1. The four routes of hydrogen production by electrolysis at present can be roughly divided into three types: industrial by-product hydrogen, fossil fuel hydrogen production and electrolytic water hydrogen production.

Industrial byproduct hydrogen means that hydrogen, as a by-product, is produced in other industrial production processes. But it is clear that hydrogen obtained in this way cannot support the development of it into an energy carrier whose production capacity is completely uncontrollable and cannot be truly industrialised.

Hydrogen production from fossil fuel, which uses coal or natural gas as raw material, is the most important way to produce hydrogen with mature process and low cost. This method has carbon emissions, does not meet the goal of carbon neutralization, and can not be used as a production process to support the hydrogen energy industry.

If supplemented by carbon capture and collection technology, hydrogen produced with zero emissions is blue hydrogen. The problem with this model is that companies have to bear a lot of extra costs, are not economical enough, and blue hydrogen is essentially not separated from fossil fuels, there is no fundamental problem. No wonder even Germany, which is quite aggressive on emissions, calls this route "confusing".

Hydrogen production from electrolytic water accounts for a low proportion in the current hydrogen production structure, but it has been widely concerned by the global energy industry. The raw material of hydrogen production from electrolytic water is easy to obtain, and the production process does not produce additional carbon emissions, which meets the double carbon goal; hydrogen energy matches the background of the rapid growth of wind power and photovoltaic installations around the world, and extremely cheap electricity greatly reduces the energy cost of hydrogen production. The ability to absorb green power also meets the needs of the renewable energy industry, and it is an ideal energy carrier under the trend of energy transformation. Nowadays, the global hydrogen production industry is developing rapidly. Energy storage, industrial production (such as steelmaking) and other industries outside the field of transportation have also been included in the development planning and set corresponding development goals in many countries, which has become one of the development directions of the energy industry.

Data show that global direct investment in hydrogen energy is nearly $250 billion by the end of 2022, while the International hydrogen Energy Commission predicts that the total investment will rise to $500 billion by 2030 [1].

In China, the medium-and long-term Plan for the Development of hydrogen Energy Industry (2021-2035) jointly issued by the National Energy Administration was issued in March 2022, which sets the development goals of the industry. However, only from January to February in 2023, a total of 8 green hydrogen projects in electrolytic cells have been invited for public bidding, with a total bidding volume of 763.5MW, an increase of nearly 3 times compared with the same period last year, and has exceeded the domestic electrolytic cell shipments in 2022 (near 750MW) [2]. Although the bidding volume and shipments are not completely comparable, the growth of shipments for the whole year is only a question of how fast they can be.

Other emerging technologies for hydrogen production from renewable energy, such as biological hydrogen production and photodecomposition hydrogen production, are not discussed because of their low maturity and far away from commercialization.

At present, there are four main hydrogen production technologies: alkaline electrolysis (alkaline water electrolysis,AWE), anion exchange membrane electrolysis (anion exchange membrane electrolysis,AEM), proton membrane electrolysis (proton exchange membrane electrolysis,PEM), and solid oxide-based electrolysis (solid oxide electrolysis cells,SOEC) [3] [4] [5]:

Hydrogen production by alkaline electrolysis: AWE uses alkaline aqueous solution as electrolyte and PPS membrane (polyphenylene sulfide) as diaphragm. Under the action of direct current, electrolysis of water to hydrogen and oxygen is the most mature, commercialized and widely used hydrogen production technology, and it is also the preferred technology route for hydrogen energy industry at present. As we mentioned earlier, the bidding volume of electrolytic cells in the first two months of 2023 has exceeded the annual shipments in 2022, and these electrolytic cells are all alkaline electrolytic cells. The advantages of AWE technology are friendly cost, simple operation, long service life of equipment, mature technology, high production capacity of single equipment and high localization rate, and the domestic equipment has reached the international leading level. The defect of this route is that the equipment is large and needs a larger site; the absolute energy efficiency is significantly lower than that of other technical routes; because the reaction process involves alkaline solution, there is a certain corrosiveness, so the equipment needs to be maintained. The most prominent disadvantage of AWE is that due to the characteristics of some production links, the response speed of the equipment is slow, it is unable to start and stop quickly, and the speed of hydrogen production is difficult to adjust, which does not adapt to the highly volatile power supply, in other words, it is difficult to cooperate with renewable energy such as wind power and photovoltaic.

Hydrogen production by anion exchange membrane electrolysis: AEM is a preparation process developed for AWE defects. The equipment uses anion exchange membrane as diaphragm and pure water or weak lye as electrolyte to realize the transport of OH- from cathode to anode. This technology has low cost, and the diaphragm has good air tightness, stability and low resistance. It can cooperate with non-precious metal catalyst to achieve high conductivity and high current density, and can alleviate the gas string problem of AWE. It is one of the possible improvement schemes of AWE. Its disadvantages are low ionic conductivity and poor stability at high temperature, so it is necessary to further research and develop efficient and stable diaphragm and suitable high performance catalyst. At this stage, AEM has the lowest technological maturity among the four routes and is still in the stage of laboratory development.

Hydrogen production by proton membrane electrolysis: PEM uses polymer proton exchange membrane to replace the diaphragm and liquid electrolyte in alkaline electrolytic cell and decomposes pure water directly. It is regarded as the next generation hydrogen production technology which is expected to replace AWE and has been commercialized in some countries. The advantage of PEM is that the equipment is small, the efficiency is high, the purity of hydrogen is high, and the response speed is fast, so it can adapt to the characteristics of large fluctuation of renewable energy, so it is very suitable to participate in the load regulation of power grid. The defect of PEM lies in the general life of equipment and higher requirements for water quality, which leads to the difficulty of raw material supply, and the production capacity of single equipment is far less than that of AWE route; at present, the core proton membrane is controlled by foreign enterprises, and the risk of low localization rate can not be ignored. The most prominent problem of PEM is that it is very expensive, the catalyst uses a large number of precious metals such as platinum, and the equipment cost can even reach 3 to 5 times that of the AWE route, which is not economical enough, and the high cost even causes some countries to turn to the AWE route in order to achieve mass production as soon as possible.

Solid oxide electrolysis of water to produce hydrogen: SOEC uses solid oxide as electrolyte. At a high temperature of 700-1000 degrees Celsius, water vapor mixed with a small amount of hydrogen enters from the cathode, and the electrolytic reaction occurs in the cathode to decompose into H2 and O2. O2-reaches the anode through the electrolyte layer, and loses electrons in the anode to form O2. SOEC is obviously different from the previous hydrogen production technology in terms of electrolytic device design and working conditions, and its advantage is that the energy efficiency is significantly higher than that of AWE and PEM, which can reach more than 90%, but the technology maturity is low, it does not have the conditions for commercialization, and is currently in the preliminary demonstration stage.

In terms of market, China is not only the largest hydrogen producer in the world, but also the largest manufacturer of electrolytic cell equipment. Of course, hydrogen at this stage does not exist as an energy carrier, but as an industrial raw material, which is widely used in oil refining, ammonia synthesis, methanol synthesis, steelmaking and so on.

According to the statistics of the International Energy Agency, the global hydrogen production capacity in 2021 is about 94 million tons, and the domestic production is about 33 million tons [6] [7]. However, the global hydrogen supply is mainly made from fossil fuel reforming, which produces a lot of carbon emissions and is not clean. This means that combined with the dual-carbon goal, even if hydrogen is not regarded as a fuel, there are alternative opportunities and commercial scenarios for hydrogen production from electrolytic water, and there is no need to limit the perspective to the hydrogen industry.

According to the annual blue book of China's hydrogen energy and fuel cell industry (2022), the global electrolytic cell market shipments reached 1GW in 2022. China's total electrolytic cell shipments exceeded 800MW, an increase of more than 129% over the same period last year, accounting for more than 80% of the world. Alkaline electrolytic cells occupy an absolutely dominant position, with annual shipments of 776MW. The top three hydrogen production equipment manufacturers with shipments are: Cockleer Competition, China Shipbuilding Piri hydrogen Energy, Longji hydrogen Energy. Among them, Longji hydrogen energy rose from the top five to the third [8] [9] in just one year.

2. Alkaline electrolytic cell: it is not difficult to understand that the mature charming AWE electrolytic cell can be favored by the market. Mature technology and low cost have always been the favorite characteristics of industrial production.

Picture source: research progress of advanced hydrogen production principles and technologies under the background of carbon neutralization [5] as a technology with a history of more than a century, the AWE route now has a high level of industrial maturity and localization. Although there is still room for cost reduction by optimizing equipment, the effect will not be particularly prominent, which is very different from the PEM route with high equipment costs. Alkaline electrolytic cell of the current core cost reduction logic has entered the pursuit of large-scale effect dilution cost stage, its typical performance is that the equipment is getting larger and larger, single cell capacity 1000Nm ³/ h has basically become standard, China ship Perry in December 2022 is to launch a single hydrogen production 2000Nm ³/ h "Big Mac" [10].

In addition to the large-scale effect, there is also room for improvement in the preparation of AWE.

The first is the upgrade of the core component, the diaphragm. At present, the equipment manufacturer is changing from the traditional PPS membrane to the composite diaphragm with better comprehensive performance.

Some composite diaphragms focus on improving the energy efficiency of AWE. BloombergNEF data show that some composite diaphragms can increase energy efficiency by 4%, and the cost of domestic membranes may only be about 30% of those in Europe, effectively continuing the price advantage of domestic equipment [11].

Other composite diaphragms try to solve the problem of gas string in alkaline electrolytic cell. In the process of hydrogen production in AWE, pressure imbalance will occur on both sides of the diaphragm due to gas production. If the hydrogen is not properly controlled, it will penetrate the diaphragm and mix with oxygen, which is extremely dangerous, so pressure management must be carried out in the process of hydrogen production. In fact, it is this kind of demand that makes the alkaline electrolytic cell difficult to adapt to the fluctuating power supply. The idea of some diaphragm manufacturers is to physically solve hydrogen leakage by producing diaphragms with excellent gas barrier, thus giving the electrolytic cell the ability to adapt to fluctuating energy.

In essence, the anion exchange membrane electrolyzer follows the AWE route after the upgrade of the diaphragm.

The high temperature of hydrogen production by alkaline electrolysis of water is also a possible upgrading direction. To sum up, running under the conditions of high temperature and high pressure can effectively improve the operation efficiency of the electrolytic cell. However, high temperature and high concentration of electrolyte will cause alkali corrosion, resulting in a decline in the service life of equipment, so high temperature needs to be matched with more corrosion-resistant materials; high pressure brings the difficulty of system management. At present, the high temperature process is still in the laboratory stage.

The study of hydrogen production from seawater is not uncommon. Coastal and offshore wind power and solar energy resources are rich, and the water resources are almost unlimited, so it is an ideal place for renewable energy in-situ hydrogen production. The current problem is that the composition of seawater is very complex, in which ions will have a variety of chemical reactions with alkaline solution, seriously affecting the operation of hydrogen production equipment. Although the mode of hydrogen production after purification of seawater onshore may not necessarily incur excessive additional costs, the offshore situation is completely different. The construction cost of building a platform at sea is very high, and the installation of additional desalination equipment will lead to a surge in costs, further reducing the already poor economy. The development of equipment capable of direct electrolysis of seawater is also the direction of researchers and enterprises.

Another idea is to optimize the control system, establish a model that can adapt to the fluctuating power supply, and upgrade the operation strategy without upgrading the hydrogen production equipment to avoid repeated start-up and shutdown and achieve stable operation.

What is more simple and direct is to connect the renewable energy to the energy storage equipment, stabilize the fluctuation directly at the power generation end, and then connect to the hydrogen production line. The advantage is that the project can be landed quickly, and the defect is that it will raise the cost of hydrogen production.

It is conceivable that if the above-mentioned and unmentioned technology upgrades can be implemented, AWE hydrogen production will be largely connected to extremely cheap energy, improve economy and lay a solid foundation for the promotion of the hydrogen industry. Furthermore, at present, the autonomy and technology accumulation of alkaline electrolytic cell route in China is significantly better than that of PEM route. Instead of competing with overseas enterprises in technological routes that they are not very good at, it is also a very common way of competition to dig deep into strong areas.

3. Proton exchange membrane: the core component of domestic opportunity PEM hydrogen production, the situation of proton exchange membrane is more complicated.

The mainstream proton exchange membrane is the end product of organic fluorine chemical industry, which has specific proton transfer function. in addition to hydrogen production, it is also a key component of hydrogen fuel cell and the same hot liquid flow cell.

Compared with AWE hydrogen production, there is a certain gap between China and foreign advanced level in PEM hydrogen production route. The technical barrier of proton membrane is relatively high. at present, China is relatively dependent on imports, the localization rate is low, and there is a certain risk of neck jam. Of course, the corresponding opportunities for localization are also more abundant. Superimposed with broader application space, policy-driven demand growth, and higher profit margins as a high-tech product, proton membrane can be considered as a market that is expected to grow rapidly.

This paper is mainly from the perspective of hydrogen production equipment, so without additional instructions below, it refers to proton exchange membrane for electrolytic cell by default.

According to the basic principle, the electrochemical process in the PEM electrolyzer is as follows: pure water enters the catalytic layer through the influent channel. Under the combined action of DC power supply and catalyst, the anode produces oxygen and hydrogen ions, and hydrogen ions pass through the proton exchange membrane and combine with the cathode to produce hydrogen. The structure of PEM electrolytic cell is shown in the following figure, which is mainly composed of bipolar plate, porous diffusion layer, proton exchange membrane and cathode and anode catalytic layer [5].

Picture source: research progress of advanced hydrogen production principle and technology under the background of carbon neutralization [5] fuel cell is the reverse reaction device of PEM electrolytic cell, which electrolyzes water into hydrogen and oxygen, while fuel cell uses hydrogen and oxygen as anode and cathode reaction material, and finally produces water and electricity.

Picture source: energy sector [12] although both electrolytic cells and fuel cells work on proton membranes and have similar structures, the product requirements are different, the performance indicators are different, and the material systems of the final products are also very different, so they cannot be generalized.

The overall structure of the electrolytic cell is relatively simple, but the working condition is worse, which requires higher service life and durability of the material, so that the membrane for the electrolytic cell is thicker than that for the battery. For fuel cells, proton membranes need to be enhanced by additional modification. For example, Gore uses expanded polytetrafluoroethylene (ePTFE) as a reinforcement material to produce ultra-thin proton membranes for Toyota, Hyundai and Honda fuel cell vehicles [13].

This shows that when evaluating products, we also need to combine the specific downstream application scenarios, and we should not simply think that proton membranes have the ability to cover multiple fields just because one enterprise produces proton membranes. There are still some differences.

It should be noted that the equipment cost of the PEM electrolytic cell is the main reason for the high cost, and the proton exchange membrane is also the core part of the electrolytic cell, but the proportion in the total cost of hydrogen production is not high (about 2.3%), and the effect of localization on cost reduction is not prominent. The main significance of localization is not only business opportunities, but also to avoid foreign restrictions in key links.

Photo Source: IRENA [14] Proton Exchange membrane products are mainly distinguished by fluorine content, which can be divided into four categories: perfluorinated proton exchange membrane, partially fluorinated polymer proton exchange membrane, non-fluorinated polymer proton exchange membrane and composite proton exchange membrane. Among them, the perfluorosulfonic acid proton exchange membrane is the most mature, the comprehensive performance is the best, and the commercial application is the most extensive. Perfluorosulfonic acid membrane is used in PEM electrolytic cell.

From the perspective of industrial chain, the upstream of proton exchange membrane is the monomer material of organic fluorine chemical industry, and the most mainstream direct product material is perfluorosulfonic acid resin material, which extends upward to tetrafluoroethylene, perfluoroalkyl vinyl ether and other monomer materials in organic fluorine chemical industry. upward traceability can be traced back to fluorite, hydrogen fluoride, refrigerants and other raw materials [15].

At present, the production process of proton exchange membrane can be divided into two categories: melt film forming method (melt extrusion method) and solution film forming method, among which solution film forming method is widely used commercially. Solution film forming method can be further subdivided into solution casting method, solution casting method and sol-gel method, with solution casting as the mainstream [15].

Due to the lack of technology, the domestic production rate of proton exchange membranes in various fields is not high and is in the catch-up stage.

The global proton exchange membrane production capacity is basically monopolized by foreign countries. For a long time, the production of perfluorinated proton exchange membrane is mainly concentrated in the United States, Japan and other developed countries, including American DuPont, Dow, Gore, Asahi Niazi, Asahi Kasei and other companies. In the field of proton membrane, DuPont has the most competitive products and the most abundant technology accumulation, while the fuel cell membrane electrode is dominated by Gore. Domestically, Dongyue Group is the industry leader, and Ke run new materials also have proton membrane products that achieve mass production.

Proton membrane is more difficult from the preparation stage of raw materials. Perfluorosulfonic acid resin is a kind of substance with very complex preparation process, which can be called the technical peak of fluorine chemical industry chain. Its production process involves a large number of harsh reaction conditions, complicated processes and explosive dangerous goods. How to produce membrane materials with chemical stability, mechanical strength, electrochemical performance and other indicators to meet the downstream needs has put forward a very high standard for enterprises. The proton membrane forming process is even more difficult, and there are strict requirements for the management of equipment, workshop and production line. In addition, affected by the first-mover advantage, Japanese and American enterprises hold a large number of key patents in the field of proton membrane. How to build their own professional system and bypass professional barriers is also a difficult problem for domestic enterprises.

In order to catch up with the international advanced level, the talent, technology accumulation and adequate capital expenditure of the local industry are essential. at the same time, foreign leading enterprises will also bring great pressure to domestic enterprises. The difficulties encountered by China's hydrogen production equipment in proton exchange membranes are very similar to those in the photoresist industry, which stems from China's late-developing disadvantages in the field of special chemicals, which will take time to make up.

In terms of market share, in terms of the domestic production rate of proton exchange membranes for fuel cells, GGII data show that the demand for proton exchange membranes for domestic membrane electrodes in 2020 is 44000m2, of which the market share of domestic proton exchange membranes is 7.5%, rising to 11.61% from 2021 [17].

PEM hydrogen electrolysis proton exchange membrane market is small, the share is occupied by Comu (formerly DuPont) Nafion ™series membranes, the market share in 2021 is as high as 76%, and the market share of domestic proton exchange membranes is 21.45%. GGII research shows that Dongyue Future hydrogen Energy, a subsidiary of Dongyue Group, has completed the pre-application verification of some customers and began to replace it domestically in 2021, with a market share of about 15% [17].

In 2021, the localization rate of proton exchange membranes for liquid flow batteries in the Chinese market is about 23.15%. The main production enterprises are Kerun new materials and Dongyue future hydrogen energy, and the proton exchange membranes of other domestic enterprises are in the sample delivery verification stage. The domestic market is still dominated by Comu's perfluorosulfonic acid resin film, with a market share of 75% [17].

Finally, although at the beginning of this section we mentioned that proton exchange membrane has a strong growth, but this only describes its growth potential, the absolute market size is not very large, the future growth is facing more uncertainty.

Theoretically, hydrogen vehicles should be the industry with the largest consumption of proton exchange membranes. According to Citic Securities, when the number of fuel cell vehicles reaches 1 million in 2030, the corresponding proton exchange membrane market space can reach 13.2 billion yuan [15]. However, we still have to consider that the growth prospect of fuel cell vehicles is not very clear, at least at present, it is far less competitive than lithium battery electric vehicles, and there are only a few applications in the field of commercial vehicles, and most of these applications are for demonstration purposes. It doesn't necessarily have a decisive advantage over electric commercial vehicles.

The market of proton membrane corresponding to PEM electrolytic cell is limited. The agency predicts that the market size of the electrolytic cell will be 35 billion by 2025, so it is estimated that under the condition that the cost structure does not change greatly, and the PEM route completely occupies the market, the corresponding proton membrane market is about 1.75 billion yuan, and the actual situation may only be much less than this figure [18]. In addition, industrial production has never been very interested in whether the technology is advanced or not, and if PEM can never compete with the AWE route at the cost level, it will not be the best route for the hydrogen production industry as a whole, and its market share will be smaller.

Vanadium flow battery is one of the hot technical routes of liquid flow battery. it is mainly concerned by the market as a potential long-term energy storage technology. The "implementation Plan for the New Energy Storage Development of the 14th five-year Plan" released in March 2022 brings the 100 megawatt liquid flow battery technology into one of the key directions of the new energy storage core technology and equipment [19]. Proton exchange membrane, or ion exchange membrane (the specific name is related to the application field), is used in the stack to block vanadium ions of different valence states and to let hydrogen ions through. By the end of October 2022, the total scale of all-vanadium flow battery projects, including filing, construction, construction under construction, winning the bid, bidding and so on, has reached 1.3GW / 5.4GWh. Among them, the projects that have already started, won the bid and are under construction exceed the 2.0GWh and are expected to be gradually landed in 2023 [20].

However, the current energy storage routes are numerous, there is no definite winner, and the corresponding technology choices for different energy storage scenarios may be different, so there is still great uncertainty about the commercialization of all-vanadium flow batteries.

In addition to the above application scenarios, proton exchange membranes have a less well-known downstream, chlor-alkali industry. More strictly speaking, this kind of organic fluorination membrane should be widely used in chlor-alkali industry as ionic membrane. Ionic membrane process is the most mainstream production process in chlor-alkali industry, including China, with the advantages of low power consumption, high liquid alkali concentration, high degree of production automation, less environmental pollution and so on. The utilization rate is close to 100% [15]. Perfluorinated ion exchange membrane is the core material, which is composed of perfluorosulfonic acid membrane, perfluorocarboxylic acid membrane and polytetrafluoroethylene reinforced mesh cloth. Because chlor-alkali is a very typical industry with high energy consumption, it is extremely difficult to expand production, it is a standard stock market, and the demand is relatively fixed. It is estimated that even if the domestic substitution is fully realized, the corresponding scale is only about 450 million, which has not received widespread attention. It's also reasonable [21].

4. Routine cooling at the end of the article, we still have to routinely throw out a basin of cold water.

Hydrogen energy is good, of course, but it is also immature. Although there are a few applications in the current energy industry, as an industry, hydrogen energy is far from enough to support the vision it portrays.

The immature constraints of hydrogen energy are not limited to the links of hydrogen production, but there are some other problems, such as storage and transportation, filling, specific commercial landing, and supporting facilities construction.

But what we see is often some enterprises, investment institutions, and even the media, which devote a lot of attention and capital expenditure to the terminal, but intentionally or unintentionally ignore the systematic development of the industry. This is not difficult to understand, after all, compared with other links, fuel cells are the simplest, and there are traces to follow-there are probably not a few people who touch lithium electricity to cross the river and try to "throw out the next Ningde era."

However, it is hard to imagine how hydrogen can create a Ningde-era leader out of thin air without a nationwide power grid and mature battery production processes. Before the lack of mature industrial chain and systematic industrial structure, it is not realistic to try to make a big brick in front of a certain link. What's more, readers must have their own judgment on how many players of hydrogen energy are just following the trend, getting hot spots, persuading investors, or even entering the low-tech threshold link of the hydrogen energy industry in order to cheat.

Furthermore, hydrogen energy is just one of many promising routes. Although it has a series of advantages such as cleanliness and high calorific value, the current wave of transformation of the global energy market is at a time when the eight Immortals are crossing the sea, and there is a lot of uncertainty about the future mainstream technology route, so there is no reason to think that hydrogen energy can definitely win and become the dominant force in the future market. No matter how big the cake is, at least it is only painted at this stage.

Hydrogen energy certainly has its positive significance, but the development of the industry is unlikely to succeed in one battle. It is hoped that the participants and promoters of the industry can look at the objective law of development more rationally. Eager for quick success and short-sightedness are synonymous in many cases, and the most likely thing to usher in is the old fist of the market.

References:

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This article comes from the official account of Wechat: fruit Shell hard Technology (ID:guokr233), author: Chen Qianlei

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