China Nonferrous Metallurgy

Abstract:Hydrogen energy is an important technical way to achieve the “Carbon Peak and Carbon Neutralization Goals”, but due to the economic bottleneck of electrolytic water technology and the safety risks of storage and transportation, the industrial application of green hydrogen has not been widely popularized. As a medium of hydrogen energy carrier, ammonia is a high-quality zero-carbon fuel, which has the inherent potential of reducing agent, and is easy to store and transport. Many scholars have done research and development on ammonia energy technology. At present, the application or research of ammonia as energy heating and smelting reducing agent in the field of non-ferrous metal smelting is still at the blank stage. Based on the analysis of the production, storage and transportation of ammonia, the fuel properties of ammonia and the reduction properties of ammonia, the reduction thermodynamics of 6 common non-ferrous metal oxides such as copper, zinc, lead, nickel, tin and antimony have been calculated. The results show that the standard Gibbs free energy of ammonia reduction is close to that of carbon reduction. In the future, it is also necessary to conduct in-depth studies on the reduction kinetics, gas-liquid interface reaction mechanism, reduction rate control link, reduction kinetics model and deeper reduction mechanism of non-ferrous metal materials reduced by ammonia, in order to provide theoretical basis for the application of ammonia in the field of non-ferrous metal smelting. In addition, the construction of low-cost green ammonia supply chain and the development of ammonia zero-carbon combustion technology and ammonia metallurgy technology system with independent intellectual property rights will be of great significance to the low-carbon development of China's smelting industry.

Abstract:At present, domestic and foreign titanium manufacturers use Kroll method to produce sponge titanium, and then use vacuum melting and casting to produce titanium and titanium alloy. This method has long process, high energy consumption, and batch production. The product cost is high, which limits the application and promotion of titanium metal.The TiO2 molten salt electrolysis method ( FFC method ) concerned by many scholars has the advantages of simple process flow and environmental friendly, but it is still not mature enough in technology, and needs further exploration and improvement.Based on the mechanism of Kroll method, a new continuous manufacturing process of titanium and titanium alloy was designed by using TiCl4 as raw material, Mg as reducing agent, and different reaction furnaces and furnace temperatures. The process uses a three-stage vertical nozzle to fully mix and contact react liquid TiCl4 with liquid Mg, and the reaction rate is high. The impurities in the liquid metal titanium or titanium alloy enter the reaction furnace gas under the vacuum condition of the reaction furnace or refining furnace, so that the purity of the product can be improved. The premise of this process is that the production scale is large, a large amount of Ti liquid or Ti alloy liquid can be continuously produced, and the Ti liquid one-time forming continuous casting technology can be realized in the Ar gas sealed chamber, which has the advantages of high production efficiency, large production capacity, high product quality, low processing cost and easy to realize intelligence. The successful development of this process can not only greatly reduce the production cost of titanium and titanium alloy materials, but also rapidly expand the application range of titanium and titanium alloy materials.

Abstract:Vanadium titanium magnetite produces a large amount of smelting slag in the blast furnace smelting process, and the titanium content of the smelting slag reaches 20%~30%. The resource utilization of vanadium titanium magnetite or titanium resources in the smelting slag has always been an important research topic. In the present work, we referred to the titanium leaching-solvent extraction process. In view of the problems of the existing extraction system, such as long extraction equilibrium time, low titanium extraction rate, equipment corrosion, difficulty in separating aqueous phase and organic phase, the mechanically activated vanadium titanium magnetite blast furnace slag is first leached with hydrochloric acid, then, a synergistic extraction system consisting of tributyl phosphate (TBP) and di (2-ethylhexyl) phosphoric acid (P204) was used (with sulfonated kerosene as the diluent) to extract titanium from the leaching solution. The experiment investigated the effects of the total concentration of extractant, extraction temperature, extraction ratio (O/A), the ratio of extractant TBP to P204, and the concentration of chloride ions on the titanium extraction rate. At the same time, the slope method was employed to preliminarily explore the extraction mechanism. The following conclusions were obtained: under optimal extraction conditions such as chloride ion concentration of 8mol/L, at the ratio of extractants TBP∶P204=1∶4, extraction time 20 minutes, extraction temperature 30℃, extraction ratio (O/A) 1∶1, the titanium extraction rate can reach over 98%. The slope method study on the extraction mechanism shows that the composition of the extract may be [TiOCl₂][HA]₂[HB]₂, and its extraction chemical reaction equation can be rewritten as:TiO²⁺+2HA+2HB+2Cl^-→[TiOCl₂][HA]₂[HB]₂.

Abstract:About 4 million tons of titanium-bearing blast furnace slag is produced domestically each year, and currently stockpiles have been exceeded 80 million tons. TiO₂ content in the titanium-bearing high slag from west region of Panzhihua is greater than 20% and has higher utilization value. Currently extracted titanium products mainly include the following several technical branches: the preparation of TiO₂, the preparation of TiC/TiCI4 and the preparation of titanium alloys. Technical introduction and state of application of the three technical branches are described herein. Patent application, applicant type, the main applicant, international patent classification and cited times are analyzed from the patent perspective. On this basis, research and judgment of the future development of titanium extraction technology on the titanium bearing blast furnace slag are made. The technical research on the Ti-extracting product with TiO₂ will be the focus in the future, technology of Ti-extracting by selective precipitation separation or by acid soak hydrolysis hydrometallurgy will be the main process technology, and improving efficiency of Ti-extracting, or reducing acid consumption or pollution on environment by improving process of separation, acid leaching or hydrolysis will be the main direction of researching; The technical research on the Ti-extracting product with TiC/TiCl4 will be based on high temperature reduction, and will be purposed on improving titanium conversion efficiency and production efficiency. The technical research on the Ti-extracting product with Ti alloy will be focused on changing reducing agent, improving process of producing metal Ti, or widening the product range of Ti alloy.

Abstract:Although the existing copper electrolyte purification method can remove arsenic, but there are still problems such as environmental pollution, high energy consumption, and high content of antimony and bismuth.In this paper, based on the mechanism of Ti—As—O chemical bond bonding, a process of titanium-based precipitant removing arsenic, arsenic-containing slag alkali leaching regeneration, regenerated precipitant acidification removing sodium, preparing metal arsenic was investigated.The better process parameters of arsenic removal process are as follows: the addition amount of titanium oxysulfate-sulfuric acid hydrate is 1.2 times of the total arsenic mass, the reaction temperature is 40℃, and the reaction time is 8h. Under this condition, the initial arsenic removal rate reaches about 60%.The optimum process parameters of alkali leaching regeneration process of arsenic sediment are as follows: liquid-solid ratio 20∶1, NaOH concentration 25g/L, reaction temperature 80℃, reaction time 1.5h. Under these conditions, the leaching rate of arsenic is 65.3%, and the arsenic removal rate reaches 50.6% in one cycle. The optimum process parameters for acidizing removing sodium of regenerated precipitant are as follows: liquid-solid ratio 2∶1, end-point pH=3.0, room temperature, reaction time 1h. Under these conditions, the sodium content in the acidized liquid is 926mg/L, and the titanium content is 0.21mg/L. The optimum process parameters for the preparation of metal arsenic are as follows: hydrazine hydrate excess coefficient 3 times, dilution multiple 5 times, reaction temperature 80℃, solution pH=7.0, reaction time 2h. Under these conditions, the reduction rate of arsenic is about 75%, and the purity of metal arsenic is about 93%.The process is simple in operation and has high selectivity for the removal of arsenic and antimony; the solution after arsenic removal can be returned to the copper electrolysis system; the arsenic-containing alkaline leaching solution can be reduced to prepare metal arsenic.The multiple cycle arsenic removal rate is maintained at about 50%, which does not cause the loss of valuable metals such as copper. Further screening of arsenic precipitation agents and reducing agents is needed to reduce the cost of agents.

Abstract:There are valuable elements such as gold, silver, lead, bismuth, arsenic, selenium and tellurium in Venturi sludge. When it is returned to Kaldor furnace for smelting, tellurium forms compounds with gold and silver in Venturi sludge, and enter smelting slag, resulting in loss. If tellurium is removed before Venturi sludge returning to Kaldo furnace, not only the tellurium resource is recycled, but also the gold and silver recovery rate is increased. In this paper, by using the inhibition of lead leaching by sodium sulfide, the experiment of NaOH-Na2S leaching Venturi sludge and preparation of tellurium dioxide and crude selenium was carried out. The following conclusions are obtained. The leaching rate of tellurium and selenium can reach 90.06% and 30.58% respectively under the optimum conditions of sodium hydroxide concentration of 100g/L, sodium sulfide addition of 4%, reaction temperature of 80℃ and alkali leaching for 2h. Compared with the process without sodium sulfide, the quality of crude tellurium dioxide can be increased from 80% to more than 90%. The results of kinetic analysis show that the leaching of tellurium in the sulfide alkali leaching stage of Venturi sludge is controlled by the diffusion model. This process can not only improve the recovery rate of gold and silver, recover tellurium resources, but also improve the production efficiency. The purity of tellurium dioxide produced is more than 99%, and the purity of crude selenium by-product is more than 90%. The economic benefit is remarkable.

Abstract:High purity tellurium is a key semiconductor material widely used in infrared detection, nuclear radiation detection, photovoltaic, refrigeration and other fields. Its application range is limited by the purity of tellurium. At present, the mainstream process for preparing 6N and 7N high-purity tellurium is vacuum distillation-hydrogen zone melting process, but for high-selenium raw materials, the products prepared by this process are difficult to meet the standards. In this paper, 4N grade tellurium was used as raw material (the main impurity elements were selenium and sodium, and the selenium content was 6.2×10-6), and the preparation experiment of high purity tellurium was carried out. By analyzing the difference of impurity content in the inner and outer layers at the same condensation position, it is found that there is a phenomenon of ‘slip in the condensation zone’, which causes the problem of low boiling impurity and product mixing. The experiment also shows that prolonging the preheating time of raw materials and adding high purity quartz also affect the purification of tellurium. In view of the above problems, the original process is improved. Under the conditions of prolonging the constant temperature preheating time of raw materials to 70min, pre-baking the condenser, and adding high-purity quartz fragments to the raw material, the selenium and sodium in tellurium can be efficiently separated before the hydrogen zone melting process. The improved process can prepare 6N grade high purity tellurium by one distillation without hydrogen in the vacuum distillation process, which greatly saves the manufacturing cost, and provides conditions for the preparation of 7N grade ultra-high purity tellurium with 4N grade high selenium tellurium.

Abstract:A low-grade copper sulfide ore was treated by bio-heap leaching-extraction-electrowinning method to produce cathode copper in a Fujian enterprise. The heap leaching process applies a permanent heap operation mode, generating a problem of excess acid and iron. The common practice is to neutralize the low copper raffinate after secondary extraction to a pH 7-8, however, this method reduces the current efficiency due to the high carry-over iron ions in the electrowinning solution, and also generates problems of high neutralization cost and neutralization residue storage. In order to solve the problem of excess acid and iron in bio-heap leaching at source, this paper puts forward the idea of mixing limestone particles into heap leaching ores to increase the content of acid-consuming gangue, and carries out test work with different batches of ores. The effects of limestone content ratio and spray intensity on the extractions of copper and iron, and other parameters were investigated, and the following conclusions were drawn. With the increase of the proportion of limestone ore blending, the acid consumption and the pyrite content in the leaching residue increase, indicating that the limestone can inhibit the leaching of pyrite and reduce the systems external acid production and iron production; increasing the spray intensity is helpful to avoid the drastic change of pH value, thus reducing the hydrolysis precipitation of copper and iron ions and promoting the leaching of copper and iron; limestone blending can maintain the low potential (450~550mV vs. Ag/AgCl) of the leaching system for a long time, and the lower potential helps to inhibit the oxidation of pyrite and reduce the production of external acid and iron.

Abstract:Vacuum induction melting gas atomization technology (VIGA technology) is the mainstream atomization technology for preparing high-performance spherical metal and metal alloy powders by gas atomization method. However, the details of closely coupled gas atomization mechanism are still unclear and lack of core theory. Due to the gas-liquid coupling during the VIGA powder production process in a closed and high-temperature environment, it is difficult to observe the details. This article simulates the preparation of Cu-Al-Ni alloy powder using VIG technology under different atomization pressures. Based on CFD technology, Fluent software is used to model the interaction between gas-liquid two-phase flow during the atomization process, simulating the primary and secondary crushing processes of copper aluminum nickel alloy melt under different atomization pressures during the atomization process. The simulation results show that the atomization pressure increases from 6MPa to 8MPa, the maximum velocity of the flow field increases from 470m/s to 520m/s, and the static pressure at the end of the delivery tube increases from -30kPa to 40kPa. During the primary atomization process, there is a pressure gradient in the radial pressure of the delivery tube port. The melt flows out of the delivery tube to form a liquid film, which is broken into initial droplets by the airflow at the junction of the reflux zone and the airflow expansion zone. The higher the atomization pressure, the smaller the initial droplets; the secondary atomization process is that the initial droplets continue to break, and the particle size of the powder is within 20~100μm, as the atomization pressure increases, the median particle size of the powder decrease, but the decrease is not significant; the design of VIGA equipment nozzles have a critical value, and after reaching the critical value, the various values in the flow field do not change significantly. Therefore, the reduction of powder particle size is not significant between 7MPa and 8MPa.

Abstract:In industry, molybdenum concentrate is generally treated by oxidation roasting-ammonia leaching process. Sintering often occurs in the process of molybdenum concentrate oxidation roasting in multi-hearth furnace, which causes the the furnace bed thickening and seriously affects the production. In view of this problem, this paper takes the thickening material at the bottom of the multi-hearth furnace bed of a company s as the research object, carries out detection of sample in vertical direction, and analyzes the phase composition and microstructure of the sample. The results show that the bottom layer is formed by impurity elements such as CaMoO₄, CaMoO₄ CuSO₄ and CaSO₄, as well as the phase composition of MoO₃ and MoO₂ the middle layer is mainly composed of MoO₃ and a small amount of Mo4O11, MoO₂ and CaSO₄; the top layer is mainly composed of MoO₃ and a very small amount of Mo₄O₁₁ and MoO₂. The analysis shows that a large number of impurity elements are enriched on the surface of the bottom material (SiO₂) at the initial stage of the bottom thickening material, forming the low melting point compound; as the production progresses, the low melting point compounds and molybdenum oxides are further deposited on the bottom layer to form the top layer of the bottom thickening material. With production going on, the thickening material at the bottom of the furnace is continuously deposited and thickened. By controlling the type and content of impurity elements in raw materials, roasting temperature, material stirring strength, roasting time, material thickness and other measures, the thickening speed of furnace bottom material can be reduced, the maintenance of multi-hearth furnace bed can be reduced, and the production cost can be saved.

Abstract:In the production process of rare earth metal praseodymium neodymium, it is easy to form nodules at the bottom of the molten salt electrolytic cell, which not only affects the continuity of production, but also affects the product quality. At present, most of the related literatures focus on the composition of nodules and the influence of electrolytic parameters on nodules. Few literatures have studied the mechanism of nodule formation. In this paper, the morphology and crystal composition of the furnace bottom nodule are analyzed. It is found that the composition of the nodule is neodymium oxide, praseodymium oxide, neodymium oxyfluoride and a small amount of neodymium fluoride and metal neodymium. The numerical simulation method was used to analyze the electrolytic flow field, and the reason for the formation of nodules at the bottom of the furnace was obtained. The main reason for the formation of nodules is that the feeding speed is too fast，and the melting point of neodymium oxyfluoride is higher than that of molten salt, and it is easy to deposit on the steps of graphite crucible to form nodules. Rare earth metals will take away a lot of heat when they leave the furnace, resulting in a large change in the temperature of the furnace bottom，and neodymium oxide is easy to precipitate in the lower temperature area and deposit on the steps of graphite crucible. The fluidity of the molten salt at the bottom of the electrolytic cell is poor, so that the products precipitated on the steps of the graphite crucible cannot be deposited with the flow of the molten salt. By controlling the feeding speed and maintaining a reasonable electrolysis temperature, excess materials or precipitated materials can be avoided to deposit on the crucible step. The growth rate of nodules can be controlled by cleaning the bottom of the furnace and the accumulated materials on the step in time.

Abstract:The annual output of copper slag in China has exceeded 20 million tons. The main mineral phases in copper slag are fayalite and magnetic iron oxide, and the iron content is more than 30 %. Due to the high thermodynamic stability of fayalite, the current recovery method needs to consume a lot of energy and the cost is high. Magnetohematite (γ-Fe₂O₃) is a metastable magnetic material with cation vacancies, which has been widely used in the fields of wastewater treatment, biomedicine and catalysis. In this paper, high purity γ-Fe₂O₃ was obtained by low temperature alkali fusion-hydrolysis-calcination process using copper slag as raw material. The results showed that the iron-bearing phase (fayalite, magnetite) in copper slag could be converted into α-NaFeO₂ precursor by calcination at 550℃; after hydrolysis and calcination, γ-Fe₂O₃ with a band gap of 2.20eV was obtained, which exhibited good photocatalytic activity in the visible light range; the specific surface area, average pore diameter, pore volume and saturation magnetization of γ-Fe₂O₃ were 9.354m²/g, 14.88nm, 0.0348cm³/g and 19.13emu/g, respectively. The photocatalytic-degradation tests of MB at room temperature showed that the photocatalytic process obeyed pseudo-first-order reaction with a degradation rate constant K value of 1.29×10^-2min^-1(20mg/L); adding H₂O₂ could improve the photodegradation efficiency; owing to its superparamagnetic, γ-Fe₂O₃ could be reused via magnetic separation and showed excellent stability in cycle photodegradation performance tests. The process uses low temperature alkali fusion and consume low energy, which provides a new way for the resource utilization of copper slag.

Abstract:Chinas annual red mud emissions are as high as 100 million tons, and the main treatment methods are landfill or storage, and there is a shortage of clay raw materials needed for the preparation of ceramics. The new CaO-MgO(10%)-SiO₂-Al₂O₃ system ceramic material has superior mechanical properties and optimistic market prospects. In this paper, the baking test of new ceramic preparation raw materials with different red mud mixing amount was designed. The microstructure and phase composition of different baked products were tested, and the physical and mechanical properties and heavy metal leaching of the products were investigated. The main phases of the samples are pyroxene phase and anorthite phase. The formation of pyroxene phase is beneficial to improve the flexural strength of the samples, and the formation of anorthite phase is beneficial to solidify sodium element and promote the densification process. The performance of the samples is similar, and they all show superior mechanical properties at 1140℃. Under the temperate, the linear shrinkage rate and bulk density are the largest, the water absorption rate is the smallest, and the flexural strength is the highest. At 30 % red mud mixing amount, the water absorption and flexural strength indexes exceeded the GB/T 4100—2015 standard. The leaching test showed that the solidification rate of each sample was as high as 99.91%, and the leaching values of seven typical heavy metals were lower than the limits of drinking water standards. This study provides a new way for the reuse of red mud in the ceramic industry. It not only solves the problem of red mud disposal, but also saves a lot of ceramic clay resources.

Abstract:The annual production of incineration fly ash in China has exceeded 1×10⁷t. Before utilization of fly ash resources, it needs to washing. The main metal components of fly ash washing solution are NaCl, KCl, CaCl₂ and other heavy metals. In this paper, hemihydrate calcium sulfate whiskers were prepared by adding sodium sulfate and crystal growth agent cetyltrimethylammonium bromide by removing impurities, detoxification and removing heavy metals from ash washing solution. The process combines the preparation of calcium sulfate hemihydrate whiskers and the treatment process of fly ash washing liquid by using an improved atmospheric pressure method. The effects of material ratio, boiling time and settling time on hemihydrate calcium sulfate whisker products were investigated. The results show that the recovery rate of Ca²⁺ can reach 95.16% under the conditions of n(calcium ion)∶n(sulfate ion)=1∶5, boiling time 1h and settling for 1.5h; the prepared hemihydrate calcium sulfate whiskers can meet the composition requirements of hemihydrate calcium sulfate whiskers in the standard of calcium sulfate whiskers (DB43/T 1155—2016)，and the products are uniform in appearance, with a length of 30~100μm, a diameter of 2~7μm, an aspect ratio up to 40, and a high density of whiskers. The process has the advantages of low production cost, environmental friendliness and easy industrial production, which provides a new solution for treatment and resource utilization of fly ash washing liquid.

Abstract:Heavy metals in wastewater have the characteristics of refractory, long-term accumulation, toxicity, metabolic difficulties and concealment, which poses a risk to the ecological environment and human health.At present, the commonly heavy metal wastewater treatment methods include dilution method, chemical precipitation method, coagulation-flocculation method and adsorption method. In this paper, the mechanism of heavy metal removal, application advantages and disadvantages and progress of these methods are introduced in detail. It is pointed out that there are some problems such as high operating cost, incomplete treatment and possible secondary pollution.It is believed that the combined treatment technology of wastewater treatment-heavy metal recovery can solve the current compound pollution problem and achieve good economic and social benefits. It is also necessary to strengthen the research on the mechanism of water treatment technology, improve the repair process of heavy metal wastewater, and develop a wastewater treatment technology within the range of heavy metal content suitable for actual discharge.In addition, it is necessary to establish a long-term ecological station for environmental detection in vulnerable areas to provide basic guarantee for the remediation of heavy metal wastewater. Attention should be paid to the environmental effects in water treatment technology evaluation to avoid secondary pollution.

Abstract:Aiming at the difficulty of producing low phosphorus molten iron in the existing smelting process of high phosphorus oolitic hematite, the oxygen-rich side-blown reduction smelting technology of high phosphorus oolitic hematite to produce low phosphorus molten iron was proposed based on raw material analysis, thermodynamic calculation, reduction smelting test and reduction system balance calculation. The following conclusions were obtained.Mineral analysis showed that high phosphorus hematite has a typical oolitic structure, and hematite was mainly distributed in the shell of concentric ring wrapping structure formed with gangue minerals, which was not conducive to the physical separation of iron oxide and gangue. Thermodynamic analysis shows that at 1450~1600℃, phosphorus elements in the high phosphorus oolitic hematite can be reduced in the form of elemental phosphorus and enter the metallic iron phase, but cannot be volatilized in the form of phosphorus oxides. Only in the presence of CaO, H₂O and CO₂ reacted with Fe₃P to bring phosphorus into the slag in the form of Ca₃(PO₄)₂. The reduction smelting test showed that the phosphorus content in molten iron produced by the thermal furnace was greater than 1.0%, while the side-blown furnace was reduced to 0.45%. The equilibrium calculation showed that the recovery of Fe decreased with the increase of O₂/CH₄ and the decrease of carbon ratio; w[C] in molten iron decreased with w[P] in molten iron. This study showed that the oxygen-rich side blowing reduction smelting technology had the advantages of the strong performance of molten pool stirring, oxygen potential regulation and temperature control, which strengthened the smelting conditions of phosphorus removal in iron and phosphorus retention in slag, so as to realize the efficient and short process treatment of phosphate-bearing iron base minerals. This paper can provide theoretical basis and process parameter guidance for the industrial application and promotion of oxygen-rich side-blown reduction smelting of high phosphorus oolitic hematite.

Abstract:Monazite is a phosphate rare earth ore with abundant light rare earth content. The decomposition rate of monazite by hot alkali leaching method can reach 97%, which has high economic benefits. At present, there are relatively few theories on the alkali decomposition of monazite, and there is a lack of research on the transformation laws of rare earth elements (Ce, Pr, Nd) in monazite. This article uses thermodynamic calculations to draw the lgc-pH equilibrium diagram of the dissolved components of alkali decomposed monazite RE-P-H₂O system (RE is La, Ce, Pr, Nd) under temperature conditions of 25℃ and 160℃. The thermodynamic equilibrium phase diagram is used to analyze alkali decomposed monazite. The results show that at 25℃, within the pH range studied, the region where LaPO₄ solid-phase stability exists is 0.08＜pH＜14.62, The region where REPO4 (RE is Ce, Pr, Nd) solid-phase stability exists is 0＜pH＜14.62; When pH ≥ 14.62, the pH values of Pr(OH)₃, Ce(OH)₃, La(OH)₃, and Nd(OH)3 precipitated sequentially are 14.62, 15.06, 15.24, and 15.46; after the system temperature increased to 160℃, the initial precipitation pH of RE(OH)₃ decreased to 10.70, and the precipitation order was Ce(OH)₃, Nd(OH)₃, La(OH)₃, Pr(OH)₃. Therefore, from theoretical analysis, it can be seen that the alkaline decomposition of solitary stones can be achieved at room temperature and pressure, and the high-temperature and high-pressure conditions have a significant promoting effect on this decomposition process, which is consistent with the existing alkaline decomposition process of solitary stones.

Abstract:Copper anode slime is a by-product of anode copper electrolytic refining, which contains a large amount of silver, selenium, copper and gold. Slime is usually melted to recover silver and gold. The melting thermodynamics of this selenium rich material has received little attention. This article uses the electromotive force method to measure the ultrafast ion conductor RbAg4I5 in solid state primary batteries as solid electrolytes. The numerical value of the standard thermodynamic function for Ag₂Se was obtained. The silver selenide was synthesized using pure elements from vacuum quartz glass ampoules as raw materials, and its homogeneity was detected using scanning electron microscopy and energy dispersive spectroscopy. Based on experimental data, Analytical equation for Ag₂Se polymorphic forms was obtained.