the industrialization of solid-state batteries is accelerating. who will be the first to benefit from it?
2024-09-13
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solid-state batteries, with their revolutionary safety and energy density, are seen as the "ultimate answer" to battery technology.
as technology continues to mature, the industrialization process of solid-state batteries in my country is accelerating, and a number of all-solid-state battery products have been launched recently.
the solid-state battery sector has become one of the few bright spots in the recent market driven by all-solid-state new products. industry insiders believe that in the process of all-solid-state battery industrialization, the most certain opportunity may be the cost reduction of raw material lithium sulfide; and semi-solid-state batteries are expected to become the transition solution from liquid batteries to all-solid-state batteries due to their high safety, high compatibility with existing production lines, simple process, and low cost. they will be put into mass production before all-solid-state batteries, bringing the first round of investment opportunities.
comprehensively surpassing liquid battery performance
solid-state batteries, as the name implies, are batteries that use solid positive and negative electrodes and solid electrolytes, which is a core difference from traditional lithium batteries that rely on liquid electrolytes. depending on the content of liquid electrolyte, solid-state batteries can be divided into three types: semi-solid (liquid electrolyte mass less than 10%), quasi-solid (liquid electrolyte mass less than 5%), and fully solid (does not contain any liquid electrolyte).
compared with liquid batteries, solid-state batteries have three main advantages in performance:
first, high energy density. solid-state batteries have a wide electrochemical window (above 5v), are compatible with more high-voltage positive electrode materials (high nickel positive electrode, nickel manganese spinel positive electrode, etc.), and can use silicon and lithium as negative electrode materials, thereby achieving higher energy density. in addition, its high voltage ratio and good safety can also simplify the battery structure and promote the improvement of battery cell energy density. the energy density of ternary iron lithium batteries is usually 180-230wh/kg. the energy density of the first generation of solid-state batteries recently released by penghui energy (300438.sz) reached 280wh/kg. weilan new energy and guoxuan high-tech (002074.sz) have developed semi-solid batteries with an energy density of 360wh/kg. high energy density brings longer cruising range. the light-year solid-state battery used in saic zhiji l6 is reported to have a cruising range of more than 1,000 kilometers.
second, it is safe. the electrolyte of lithium-ion batteries has the risk of leakage, and there is a risk of spontaneous combustion and explosion when the temperature is too high. solid electrolytes have good thermal stability, are non-flammable, non-explosive, and have no risk of liquid leakage. in addition, since the chemical activity of solid electrolytes is relatively stable, they are less affected by ambient temperature and have higher stability in collisions and extrusions. in addition, solid-state batteries have a wider temperature range and can better adapt to high and low temperature environments. penghui energy's solid-state battery products have an operating temperature range as wide as -20℃~85℃.
long cycle life. solid-state batteries use non-flammable solid electrolytes instead of flammable organic electrolytes, which can inhibit lithium dendrites from piercing the diaphragm and causing short circuits, greatly improving battery safety and cycle life. at the same time, the solid electrolyte has high mechanical strength, which can maintain structural integrity when the battery expands or contracts, and reduce battery performance degradation caused by mechanical stress. the interface compatibility between the solid electrolyte and the electrode material is better, which reduces the growth of the interface impedance and helps maintain the long-term stable charge and discharge performance of the battery. under ideal conditions, the cycle performance of the solid-state battery can reach about 45,000 times.
upgrades in positive and negative electrode materials bring iterative opportunities
based on the technical reality that the energy density of liquid batteries has reached its ceiling, solid-state batteries are believed to partially or even completely replace liquid batteries in the future. so, what are the similarities and differences between the two from the perspective of the industrial chain? what new investment opportunities will the replacement process bring?
first, let's look at the "same". from the perspective of battery structure, solid-state batteries and liquid batteries are similar in structure, both consisting of a positive electrode, a negative electrode, and an electrolyte. from the perspective of the industrial chain, the industrial chain structure of the two is also roughly the same, both including the upstream resource end, the midstream manufacturing end, and the downstream application end. from a cost perspective, battery materials are the main source of cost.
let's look at the "difference". the main difference between the two lies in the different materials used. guolian securities research report pointed out that the development and application of solid-state battery technology will present a tiered penetration in the form of "solid electrolyte → new negative electrode → new positive electrode", and the core lies in the introduction of a new material system. among them, the negative electrode material will be upgraded from graphite to silicon-based negative electrode, lithium-containing negative electrode, and metal lithium negative electrode; the positive electrode material will be upgraded from high-nickel ternary to high-voltage high-nickel ternary, ultra-high nickel ternary, and then to spinel nickel manganese oxide, layered lithium-rich base and other new positive electrode materials; the diaphragm will be upgraded from traditional diaphragm to oxide-coated diaphragm, and finally the diaphragm will be eliminated.
in terms of positive electrodes, the current lithium iron phosphate and ternary material systems can still be used, and high-voltage positive electrode materials can be used in the future to achieve higher energy density. at present, the development of solid-state battery positive electrodes is mainly concentrated in high-nickel ternary positive electrodes, lithium nickel manganese oxide, and lithium-rich manganese-based routes. among them, high-nickel ternary positive electrodes have become the current mainstream due to their high energy density, good rate performance, and high degree of commercialization. materials such as lithium-rich manganese-based and lithium nickel manganese oxide have outstanding advantages in high energy density and are expected to become a new direction in the future. among listed companies, rongke technology (688005.sh) and dangsheng technology (300073.sz) have already achieved shipments of high-nickel ternary products to solid-state battery companies, and guoxuan high-tech and byd battery (835185.bj) have also made arrangements.
in terms of negative electrodes, the negative electrode materials of solid-state batteries mainly include graphite, silicon, metallic lithium, etc., which are quite different from liquid batteries. in the short and medium term, silicon-based negative electrodes are expected to become the main solution for negative electrode materials of solid-state batteries. the theoretical specific capacity of silicon is as high as 4200mah/g, which is more than ten times the gram capacity of current graphite negative electrode materials (372mah/g). it has the advantages of low potential, high gram capacity, high energy density, sufficient resource reserves, and low cost. in the long run, metallic lithium will become the ultimate choice for the negative electrode of solid-state batteries. metallic lithium has the advantages of high theoretical gram capacity and low electrode potential, but there are still some challenges in the industrialization of metallic lithium, mainly including short circuits caused by lithium dendrites piercing the diaphragm, circuit breaks caused by volume changes during the cycle, and performance degradation caused by unstable sei films.
in terms of silicon-based negative electrodes, shanshan holdings group (600884.sh), xiangfenghua (300890.sz), putailai (603559.sh), byd battery co., ltd., and china science and technology electric co., ltd. (300035.sz) all have production capacity plans; in terms of metal lithium negative electrodes, traditional lithium resource giants such as ganfeng lithium co., ltd. (002460.sz) and tianqi lithium co., ltd. (002466.sz) are expected to enjoy market dividends brought by negative electrode iterations and demand growth in the long term.
semi-solid electrolytes increase demand for rare metals
as the primary "variable" in the application of solid-state battery technology, solid electrolytes can be mainly divided into polymer solid electrolytes and inorganic solid electrolytes according to the type of material. the representative system of the former is peo polyethylene oxide, while the latter includes oxide, sulfide and halide systems.
among them, oxide electrolytes have good thermal stability and chemical stability to lithium metal, and are usually used in semi-solid-state batteries. representative companies of this route include tdk, toyota, qingtao energy, weilan new energy, ganfeng lithium battery, farasis energy (688567.sh), guoxuan high-tech, lishen battery, and prologon technology; while sulfides have an advantage in conductivity and are considered to be a strong candidate material for all-solid-state batteries. representative companies of this route include samsung sdi, sk, lg energy solution, solidpower, panasonic, catl (300750.sz), byd (002594.sz), gac group (601238.sh), and penghui energy, etc.
in the oxide electrolyte route, according to the electrolyte crystal structure, it can be divided into perovskite structure type (such as llto), garnet structure type (such as llzo), fast ion conductor type (latp), thiophosphate (lgps), etc., which will generate new demand for metal raw materials such as zirconium, lanthanum, titanium, and germanium.
the raw materials of llzo include zirconium dioxide, zirconium nitrate, zirconium carbonate, etc. my country has a small reserve of zirconium ore resources and a large demand. the import dependence is as high as more than 90%, and the supply and demand pattern has been in a tight balance for a long time. domestic zirconium production enterprises mainly include oriental zirconium (002167.sz), sanxiang new materials (603663.sh), kaisheng technology (600552.sh), etc., and they have already carried out supporting research and development of solid-state battery materials.
the raw materials of llzo/llto include lanthanum oxide, lanthanum nitrate, lanthanum hydroxide, etc. china has rich rare earth resources, contributing 70% of the global output. shenghe resources (600392.sh) and northern rare earth (600111.sh) have the ability to produce lanthanum oxide.
the raw materials of llto/latp include titanium dioxide, titanium pyrophosphate, etc. in 2022, the global titanium resource reserves (in terms of tio2) will be about 700 million tons, mainly ilmenite; china accounts for 29% of the world's total, ranking first in the world. the main domestic titanium dioxide manufacturers include china national nuclear titanium dioxide (002145.sz), longbai group (002601.sz), vanadium titanium co., ltd. (000629.sz), etc.
the raw materials for lagp, sulfide solid electrolyte lgps, etc. include germanium dioxide, germanium sulfide, etc. the main domestic companies include yunnan germanium industry (002428.sz) and chihong zinc and germanium (600497.sh).
lithium sulfide is the key to reducing the cost of all-solid-state electrolytes
sulfide electrolytes are suitable for all-solid-state batteries. the electrolyte materials mainly include lithium sulfide (li2s), sodium sulfide (na2s), potassium sulfide (k2s) and other types. among them, the lithium sulfide route has received high attention. orient securities research report pointed out that among sulfide electrolytes with different crystal structures, considering the thermal safety characteristics, cost, process maturity and other factors, the argyrodite electrolyte lpscl (li6ps5cl) is a better technical route choice for sulfide all-solid-state batteries.
however, the high price of lithium sulfide has become the main obstacle to the commercialization of sulfide electrolytes. taking lpscl as an example, lithium sulfide is the key raw material for the synthesis of lpscl electrolytes. the current price of lithium sulfide exceeds us$650,000/ton (approximately rmb 4.63 million/ton), which is far higher than the commercialization threshold.
at present, the main production methods of lithium sulfide include mechanical ball milling, high-temperature reduction, solvent method, etc. these preparation processes have high requirements on temperature, moisture, and energy consumption, and the preparation process needs to be carried out in an inert atmosphere, resulting in high prices for lithium sulfide, which accounts for nearly 80% of the cost of sulfide solid electrolytes. in addition, sulfide solid electrolytes also face problems such as poor solid-solid interface contact leading to reduced ion transfer efficiency, easy reaction with moisture to produce toxic gases, and the need for an inert environment for production and storage. therefore, improving the preparation process of lithium sulfide has become a key factor in reducing the cost of sulfide electrolytes and even the cost of all-solid-state batteries.
listed companies that have made early arrangements for lithium sulfide may be the first to benefit from the development of all-solid-state batteries. tianqi lithium has currently completed the relevant support work for the industrialization of the next generation of lithium sulfide, and has conducted proofing with more than ten downstream customers, and has continued to carry out product quality improvement and cost reduction technology optimization; hunan enjie frontier new materials, a holding subsidiary of enjie co., ltd. (002812.sz), has completed the construction and operation of a small-scale annual production capacity of high-purity lithium sulfide products for solid-state use, and has built a pilot production line of 100 tons of lithium sulfide.
in addition, rongba technology applied for a patent involving a method for preparing lithium sulfide in december 2023. by adding an organic sulfur source, the reaction between the carbon source and lithium sulfate is promoted, the production of impurity li2o is reduced, and the purity of lithium sulfide is improved; blue ocean huateng (300484.sz)'s shareholding subsidiary high energy times has made breakthroughs in material modification. under the premise of controllable costs, it has the ability to mass-produce tons of lithium sulfide raw materials, and the phase xrd test results show that the material purity is high. the company claims that the test results of the ionic conductivity performance of the sulfide electrolyte (lipscl) are comparable to the world's top level.
(this article comes from china business network)
