Pre-intercalating agent, pre-intercalated lithium cathode, pre-intercalated sodium cathode, secondary battery containing these, and method for pre-intercalating lithium and sodium.

Abstract

The present invention provides a pre-intercalating agent used to pre-intercalate lithium or sodium having an organosulfinate structure as its backbone, a pre-intercalated lithium cathode, a pre-intercalated sodium cathode, a secondary battery, and a method for pre-intercalating lithium or sodium using the pre-intercalating agent. The pre-intercalating agent of the present invention has a high specific capacity, good stability, no residue, and good compatibility with battery systems, making it very suitable for use in lithium or sodium ion secondary batteries. The pre-intercalation process of the lithium or sodium pre-intercalation method of the present invention is safe, the production industrial technology is simple, and the cost is low, allowing for large-scale production.

Description

[Technical Field]

[0001] The present invention relates to a pre-intercalating agent, a pre-intercalated lithium cathode containing a raw material for pre-intercalating lithium, a secondary battery containing the pre-intercalated lithium cathode, and a method for pre-intercalating lithium. Furthermore, the present invention relates to a pre-intercalated sodium cathode containing a raw material for pre-intercalating sodium, a secondary battery containing the pre-intercalated sodium cathode, and a method for pre-intercalating sodium. [Background technology]

[0002] In response to the ever-increasing energy demand and serious environmental problems, developing highly efficient and reliable energy storage technologies has become an urgent task. Lithium-sodium battery technology is considered one of the most promising energy storage technologies, and its advantages such as high energy density and low cost have already led to its widespread application in electric vehicles and portable electric devices. However, with the further development of human society, the demands on storage technologies in various new applications are increasing, and lithium-sodium battery technology is currently facing the problem of insufficient energy density. Therefore, for lithium-sodium batteries, for example, silicon (4200mAh g) -1 ) and phosphorus (2596mAh g -1It is necessary to consider new lithium batteries that use high-capacity-density negative electrode materials such as ) ). However, these negative electrode materials are associated with irreversible side reactions during the charge-discharge process, resulting in lithium ion loss and a decrease in battery capacity. Silicon-based materials (SiOx), for example, undergo irreversible electrochemical reactions to generate lithiumSiOx, making them unusable. Furthermore, an interfacial film (SEI) may form on the surface of the silicon negative electrode, consuming some lithium ions. Consequently, during subsequent charging, the number of lithium ions that can return to the positive electrode decreases, resulting in a loss of battery capacity and insufficient utilization of the positive electrode material. Due to these side reactions, the initial Coulomb efficiency (ICE) and cycle efficiency (CE) of the battery are both far below 100%. Taking SiO negative electrodes as an example, the total battery ICE is only 50% to 60%, meaning the battery has already lost more than 40% of its capacity in the first cycle, severely limiting the further development of these materials. Therefore, this problem needs to be solved by pre-intercalating lithium, that is, by pre-storing a certain amount of lithium in the battery before assembly to compensate for lithium loss during the battery's first cycle. The same problem exists with sodium batteries, but to date, there are no industrially developed sodium pre-intercalating agents or methods that can stably, effectively, and well replenish sodium.

[0003] Currently, there are two relatively mature technologies for pre-intercalating lithium: one that directly incorporates the lithium source via the negative electrode, and another that adds lithium via the positive electrode. The technology that directly incorporates the lithium source via the negative electrode has high efficiency in pre-intercalating lithium and does not incorporate ineffective components, but it has high industrial technology requirements, is costly, has poor safety, and is unsuitable for large-scale production. Pre-intercalated lithium technology added via the positive electrode has the advantages of high safety and simple industrial technology requirements, but by-products may remain in the battery after lithium replenishment, which reduces the battery's energy density, easily creates pores in the positive electrode, and reduces the battery's cycle life. Therefore, there is a critical need for a positive electrode lithium replenishment technology that does not leave by-products after lithium replenishment and enhances the battery's energy storage.

[0004] Patent Document 1 discloses a method for pre-lithifying the electrodes of a lithium-sulfur battery. By pre-lithifying the sulfur positive electrode, it is possible to prevent the lithium source from being incorporated into the negative electrode. Since the conductivity of the sulfur positive electrode is relatively low and the release of heat during contact with the lithium source is relatively slow, it is advantageous in reducing potential safety problems and improving safety performance. Furthermore, by using lithium foil to pre-lithify the positive electrode, it is possible to prevent the incorporation of other substances, thus ensuring energy density and being advantageous for application to battery systems where the overall lithium source is deficient. However, Patent Document 1 requires the use of lithium metal raw materials, which are unstable in air and inconvenient to handle. In addition, the short-circuit lithium replenishment method involves a violent reaction and is difficult to control the reaction time, which can result in an unstable positive electrode interface and affect the battery's cycle performance.

[0005] Patent Document 2 discloses a two-layer composite diaphragm battery and a method for replenishing it with lithium. This method effectively avoids the inability to control the reaction rate when replenishing lithium, achieves the goal of uniformly replenishing lithium, and can significantly increase the charge-discharge efficiency and energy density of the battery in its first cycle. However, Patent Document 2 uses a three-electrode system containing lithium metal to replenish the battery with lithium. This method requires the use of lithium metal raw materials that are unstable in air and inconvenient to handle, and also requires the embedding of lithium metal electrodes between the two diaphragms. Furthermore, the incorporation of unspecified components may reduce the energy density of the battery system.

[0006] Patent Document 3 describes the sodium supplement additive Na2C x O y N z It has been reported that sodium can be replenished in sodium-ion batteries by mixing a certain ratio (5% to 20%) of a positive electrode material with a certain material to create a mixed positive electrode material. However, the materials required by the above method must undergo firing at high temperatures, which is relatively expensive, and the residual components after sodium replenishment are embedded in the battery, resulting in a decrease in the overall energy density of the battery.

[0007] Other conventional technologies include using sodium-replenishing additives such as Na5FeO4 or Na2C2O4, which are mixed with the cathode material in a certain ratio to create a mixed cathode material, thereby replenishing sodium in sodium-ion batteries. Similarly, the materials required by these methods must undergo decomposition by high voltage, which reduces the stability of the battery interface and affects the long-cycle use of the battery. In addition, residual components after sodium replenishment are embedded in the battery, resulting in a decrease in the overall energy density of the battery. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Chinese Patent Application Publication No. 116470165 Specification [Patent Document 2] Specification of Chinese Patent Application Publication No. 107845829

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0009] The object of the present invention is to provide a pre-intercalation agent, a pre-intercalated lithium / sodium cathode, a lithium / sodium ion battery containing these, and a method for pre-intercalating lithium / sodium, which have no by-products remaining in the battery after pre-intercalating lithium / sodium, good stability, are advantageous for safety in the process of pre-intercalating lithium / sodium, and have high energy density and capacity retention rate.

Means for Solving the Problems

[0010] The present invention provides an organic pre-intercalation agent with few or no residues after pre-intercalation treatment. The pre-intercalated lithium / sodium cathode of the present invention is obtained by treating with the organic pre-intercalation agent of the present invention, and the method for pre-intercalating lithium / sodium of the present invention is a method of performing a treatment of pre-intercalating lithium / sodium into the cathode using the organic pre-intercalation agent of the present invention.

Effects of the Invention

[0011] Since the side groups of the organic preintercalation agent of the present invention can be adjusted, the raw material structure can be designed by selecting various side groups. In addition, its synthesis process is simple and the cost is low. In addition, the preintercalated lithium / sodium obtained by preintercalating with the organic preintercalation agent has a high specific capacity, an appropriate lithium / sodium desorption potential, and good compatibility with the battery system. The preintercalation agent of the present invention has good stability, and the process of preintercalating lithium / sodium is advantageous in terms of safety. Since there are few residual components in the battery system, the cycle performance of the battery is not affected. The production industrial technology is simple and the cost is low, so it can be produced on a large scale.

Brief Description of the Drawings

[0012] [Figure 1] Figure 1 is a diagram showing the curves of the cyclic voltammetry test and the charge-discharge test of the sodium trifluoromethanesulfinate button-type battery in Example 1 of the present invention. [Figure 2] Figure 2 is a diagram showing the curves of the cyclic voltammetry test and the charge-discharge test of the lithium trifluoromethanesulfinate button-type battery in Example 1 of the present invention. [Figure 3] Figure 3 is a diagram comparing the in-situ Raman measurement of the method for preintercalating lithium with the lithium trifluoromethanesulfinate electrolyte in Example 1 of the present invention, and the Raman spectra of lithium trifluoromethanesulfinate powder, pure electrolyte, lithium trifluoromethanesulfinate dissolved in pure electrolyte, and after charging. [Figure 4] Figure 4 is a diagram comparing the Raman spectra of a newly manufactured sample and a sample stored in dry air of the lithium trifluoromethanesulfinate electrolyte in Example 1 of the present invention. [Figure 5] Figure 5 is a diagram showing the charge-discharge curve measurements of preintercalation agents substituted with various side groups in Examples 2, 3, 4, and 5 of the present invention. [Figure 6]Figure 6 shows the charge-discharge curve measurements of various substituents of sodium organosulfinate according to the present invention. [Figure 7] Figure 7 shows the charge and discharge efficiency in Embodiment 8 of the present invention. [Figure 8] Figure 8 shows the charge and discharge efficiency in Embodiment 9 of the present invention. [Figure 9] Figure 9 is a diagram comparing the effects of lithium supplementation in Example 10 of the present invention. [Figure 10] Figure 10 is a diagram comparing the effects of sodium replenishment using the electrolyte in Example 11 of the present invention. [Figure 11] Figure 11 is a diagram comparing the effects of coating the positive electrode surface and replenishing sodium in Example 12 of the present invention. [Figure 12] Figure 12 is a diagram comparing the effects of doping and sodium supplementation of the positive electrode in Example 13 of the present invention. [Figure 13] Figure 13 is a diagram comparing the effects of pre-intercalation of sodium in Example 14 of the present invention. [Figure 14] Figure 14 shows the efficiency of lithium being replenished multiple times with electrolyte in Example 15 of the present invention. [Modes for carrying out the invention]

[0013] The present invention will be described in detail below, but the present invention is by no means limited thereto, and any modifications can be made within the scope of the concept of the present invention.

[0014] [Pre-intercalating agent] The pre-intercalating agent of the present invention has the following organic sulfinate structure.

[0015] [ka] In formula (1) above, R is selected from alkyl groups having 1 to 10 carbon atoms and halogen-substituted alkyl groups thereof, aryl groups having a benzene ring, a thiophene ring, a furan ring, or a pyridine ring and halogen-substituted aryl groups thereof, chain ethers and cyclic ethers having 1 to 10 carbon atoms, and chain esters and cyclic esters having 1 to 10 carbon atoms. X represents Na or Li.

[0016] Preferably, R is selected from alkyl groups -Me, -Et; halogen-substituted alkyl groups -CF3, -C2F5, -C4F9; aryl groups -Ph, -CH3C6H4, -C5NH4, -C4H3S, -C4H3O; and halogen-substituted aryl groups -FC6H4, -ClC6H4.

[0017] In this invention, when X is Na, sodium can be added to a sodium-ion secondary battery, and when X is Li, lithium can be added to a lithium-ion secondary battery. The capacities of the secondary batteries after pre-intercalation treatment can reach 311 mAh / g and 262 mAh / g, respectively, and a suitable lithium / sodium desorption potential of 3.2V to 4.1V exists.

[0018] The pre-intercalating agent of the present invention generates the following reaction during the pre-intercalating of lithium / sodium.

[0019] [ka]

[0020] [ka]

[0021] As shown above, organic sulfinates have a cation-anion equilibrium, and when the anion loses electrons and undergoes oxidative decomposition, the cation is released, resulting in the replenishment of lithium and sodium. This process is related only to the oxidation potential of the anion, which is lower than 4.3V compared to lithium metal and lower than 4V compared to sodium metal, both of which are within the voltage range of normal use of lithium-sodium batteries. Therefore, X can be either lithium or sodium. Other organic structures such as organic sulfonates, organic carboxylates, organic pentafluoride phosphates, organic trifluoride borates, and organic phenolic salts cannot achieve the effects of the present invention because, when comparing the oxidation potential of the anion with that of lithium-sodium metal, it is not within the voltage range of normal use of lithium-sodium batteries.

[0022] Furthermore, by selecting R, the side groups of the organic pre-intercalating agent can be adjusted, allowing for adjustment to achieve various parameters such as voltage, solubility, and products, making it suitable for use in various battery systems. For example, as shown in the above reaction equation, when R is a methyl group or an ethyl group, the volume per gram of the pre-intercalating agent is maximized, all products are gases, the decomposition voltage is relatively low, but the solubility is relatively poor, making it suitable for use by blade coating on the surface of the positive electrode or by doping inside the positive electrode. When R is a fluorine-substituted alkyl group, the pre-intercalating agent has relatively high solubility in the electrolyte, making it suitable for use by adding it to the electrolyte. From the viewpoint of volume per gram, voltage, and solubility of the pre-intercalating agent, the fluorine-substituted alkyl group is more preferably a trifluoromethyl group.

[0023] Since the structure of the organic sulfinate depends only on the mass and volume of active lithium ions or sodium ions in the battery, the pre-intercalating agent of the present invention has high specific energy and volumetric energy density. When R is -Me, -Et, -CF3, or -C2F5, other products besides the generation of active lithium ions or sodium ions are gases and can all be discharged from the battery system. When R is any other functional group, other than the generation of active lithium ions or sodium ions, the remaining products are dissolved in the electrolyte in the form of a co-solvent and do not increase the overall volume of the battery, thus having a high volumetric energy density.

[0024] In this invention, when pre-intercalating lithium / sodium using a pre-intercalating agent having the above-described sulfinate structure, all by-products can be discharged as gas, resulting in less residue in the electrodes and preventing a decrease in the overall energy density of the battery. Therefore, when pre-intercalating lithium / sodium using an electrolyte, there is no residue, and the amount of replenishment is large, resulting in low cost, easy manufacturing, and easy storage.

[0025] The pre-intercalating agent having the structure of the above-described organic sulfinate in the present invention can be directly adopted from commercially available products. The lithium salt can also be obtained by a manufacturing method comprising the following steps.

[0026] Step (1) involves taking the commercially available sodium organic sulfinate salt mentioned above, recrystallizing it in a solvent, and obtaining a raw material for pre-intercalating sodium. Step (2) involves taking the raw material for pre-intercalating sodium in step (1) described above, placing it in an organic solvent, adding an appropriate amount of acid dropwise, stirring to allow the reaction to proceed, extracting and drying, and then evaporating and drying the solvent. Step (3) involves adding the product obtained in step (2) to deionized water, adding an appropriate amount of lithium salt, stirring to allow the reaction to proceed, and then evaporating and drying the solvent. Step (4) involves recrystallizing the solid obtained in step (3) using ethyl acetate and dichloromethane, and drying the resulting solid powder to obtain a lithium organic sulfinate salt, which is a raw material for pre-intercalating lithium.

[0027] Preferably, the solvent used in step (1) is selected from at least one of water, ethyl acetate, and ethanol.

[0028] The solvent used in step (2) above is selected from at least one of acetonitrile, tetrahydrofuran, diethyl ether, and ethanol, and these solvents are preferred because they have relatively good water solubility.

[0029] The acid used in step (2) above is selected from non-oxidizing acids such as hydrochloric acid, sulfuric acid, and acetic acid.

[0030] The lithium salt used in step (3) above is selected from water-soluble lithium salts such as lithium hydroxide, lithium carbonate, and lithium acetate.

[0031] Preferably, in step (2) above, the stirring reaction time after adding the acid is 1 to 10 hours, and in step (3) above, the stirring reaction time after adding the lithium salt is 5 to 10 hours. The drying step in the above steps may preferably be vacuum drying, at a temperature of 50 to 100°C for 10 to 24 hours.

[0032] [Method for pre-interlacing lithium / sodium] The method for pre-intercalating lithium / sodium according to the present invention can be specifically carried out by adding the above-mentioned pre-intercalating agent of the present invention to an electrolyte and performing an electrochemical reaction of charge-oxidative decomposition, or by doping the electrodes or coating the electrode surface.

[0033] The following methods can be listed for doping electrodes. The pre-intercalating agent of the present invention is mixed with the necessary positive electrode raw materials, conductive agent, binder and solvent, and polished uniformly using a polishing machine such as an agate ball mill. Then, a film coating is performed on the electrode current collector using a film coating machine to form a film, and it is vacuum dried in a vacuum dryer to obtain electrode sections of the pre-intercalating agent of the present invention having the above-mentioned sulfinate structure. The electrode sections are assembled into a pre-sealed battery, and current is applied to carry out the above-mentioned electrochemical reaction, so that the electrode sections undergo the process of pre-intercalating lithium / sodium. The pre-intercalating agent of the present invention can produce only gaseous byproducts when carrying out the electrochemical reaction, so that all byproducts are discharged as gas, and therefore, it is possible to prevent the incorporation of unspecified components.

[0034] In addition to the method described above, another advantage of the pre-intercalating agent of the present invention is that it can be used to pre-intercalate lithium / sodium into a lithium / sodium battery by dissolving it in the electrolyte of a conventional commercial battery and then pouring the electrolyte into the battery. Specifically, in this method, the pre-intercalating agent is dissolved in the battery electrolyte at a mass fraction of 0.1% to 30%, preferably 0.1% to 6%, and then the electrolyte is poured into the battery to pre-intercalate lithium / sodium into the battery. In this case, the battery electrolyte is preferably a carbonate ester electrolyte or an ether electrolyte.

[0035] When lithium and sodium are replenished using an electrolyte, the pre-intercalating agent exists in a free ionic state in the electrolyte system. During charging, a potential difference can exist between the positive and negative electrodes of the battery. Under the action of this potential difference, anions may concentrate and be adsorbed onto the surface of the positive electrode, leading to electrochemical oxidation. In this case, the cations of X are intercalated, enabling the replenishment of lithium and sodium.

[0036] The pre-intercalating agent and the method of pre-intercalating lithium / sodium using the present invention have the advantage of being able to be directly dissolved in the electrolyte of the battery, in addition to the methods of doping and coating electrodes described above. Therefore, they have good compatibility with batteries and can be effectively applied to lithium batteries and sodium batteries. In addition, when dissolved directly in the electrolyte, there is no need to dope the positive electrode, and it is added and used by directly compounding and preparing the electrolyte, so the incorporation of non-specified components can be more effectively avoided, and as a result the energy density of the battery does not decrease. Furthermore, since it can be added multiple times to used batteries, especially discarded lithium batteries, via the electrolyte, it is possible to pre-intercalate lithium / sodium in the battery multiple times, and consequently, discarded lithium batteries can be regenerated on the spot without disassembly. The process of pre-intercalating lithium / sodium by adding it via the electrolyte does not alter the structure of the battery components, such as forming many voids in the positive electrode, so a pre-intercalated lithium / sodium electrode can be obtained more stably. In addition, the method of adding the electrolyte to the battery is highly integrated with the industrial technology of battery production, so it does not require any additional costs beyond those specified, resulting in relatively low costs.

[0037] [Electrodes of lithium-ion secondary batteries] For example, as the positive and negative electrodes of a lithium-ion secondary battery, a positive electrode section and a negative electrode section can be used, which have a structure in which an active material layer containing a positive electrode active material, a negative electrode active material and a binder is formed on the current collector.

[0038] The positive electrode current collector and the negative electrode current collector of the present invention can be made of any material that can be used as a current collector for a lithium-ion battery. For example, copper can be used as the negative electrode current collector and aluminum can be used as the positive electrode current collector.

[0039] The positive electrode active material of the present invention can be any raw material that can be used as a positive electrode active material for lithium-ion batteries, for example, an organic sulfur positive electrode such as sulfur-modified polyacrylonitrile (SPAN), lithium iron phosphate, lithium cobaltate, lithium manganate, titanium disulfide, vanadium pentoxide, Prussian blue (Fe4[Fe(CN)6]3), NCM811, or other ternary raw materials.

[0040] The positive electrode may contain a binder, and any substance that can be used as a binder for positive electrodes in lithium-ion batteries in this region can be used, such as polyvinylidene fluoride (PVDF), polyacrylic acid-based binders, polyurethane-based binders, etc.

[0041] The negative electrode active material of the present invention can use any raw material that can be used as a negative electrode active material for lithium-ion batteries, for example, lithium metal, graphite, silicon-carbon, Si, or composites thereof, such as a composite of Si and graphite, a composite of Si and lithium metal, a composite of graphite and lithium metal, etc., or silicon-oxygen compounds such as silicon monoxide (SiO).

[0042] The above-mentioned active material layer may further contain a conductive agent, and examples of the conductive agent include conductive carbon Super P, carbon nanotubes (CNTs), natural graphite, artificial graphite, coke, carbon black, pyrolyte carbons, carbon fibers, roasted organic polymer compounds, and any other substance that can be commonly used as a conductive agent for lithium-ion batteries in this field.

[0043] The lithium pre-intercalating cathode of the present invention can undergo the lithium pre-intercalating process described above, which is carried out by dissolving the pre-intercalating agent shown in formula (1) of the present invention in an electrolyte and carrying out an electrochemical reaction, by doping or coating the electrode with the pre-intercalating agent shown in formula (1) of the present invention. Conventional lithium / sodium pre-intercalating electrodes require the use of lithium metal raw materials, which are unstable in air and inconvenient to handle, and the reaction is violent and difficult to control the reaction time. As a result, the interface of the cathode becomes unstable, and the battery cycle performance may be affected. However, the lithium pre-intercalating raw material having the above-described organic sulfinate structure of the present invention is stable to water and oxygen, is easy to handle, and the reaction process is mild, thus effectively avoiding the above-mentioned problems.

[0044] When calculated using a 1Ah battery, typical LFP-graphite, ternary-graphite, and lithium cobalt oxide-graphite battery systems have an initial efficiency of over 95%, and the amount of lithium replenishment required to achieve 100% efficiency is between 0.1% and 5%. In special battery systems such as lithium-free cathode-graphite and lithium-free cathode-copper, the battery system does not contain lithium ions, and the initial efficiency after 100% lithium replenishment is around 50%, and the amount of lithium replenishment required to achieve 100% efficiency is between 100% and 200%.

[0045] As described above, since the product after the pre-intercalation treatment of the present invention is either a gas or soluble in the electrolyte, there is little residue in the electrode, and the determination can be made by the amount of pre-intercalating agent in the electrode before and after the pre-intercalation treatment. When calculating the range of pre-intercalation of lithium for a battery capacity of 1Ah as 0.1% to 200%, the amount of pre-intercalating agent in the positive electrode where the lithium is pre-intercalated before the lithium pre-intercalation treatment is calculated using the formula described below, and the calculation for sodium batteries is the same as for lithium batteries.

[0046] Specifically, when calculated with a battery capacity of 1Ah, the amount c to pre-intercalate lithium relative to a battery capacity of 1Ah is 1*X%(Ah), and the volume of lithium replenisher is,

[0047]

number

[0048]

number

[0049] The pre-intercalating agent having the above-described organic sulfinate structure of the present invention can be added to used batteries multiple times via the electrolyte, thereby replenishing lithium in the battery multiple times and extending the life of the lithium-ion battery. Preferred combinations include: a combination of a graphite negative electrode and a lithium iron phosphate positive electrode; a combination of a graphite negative electrode and a ternary positive electrode; a combination of a graphite negative electrode and a lithium cobalt oxide positive electrode; a combination of a graphite negative electrode and a lithium manganese oxide positive electrode; a combination of a silicon-carbon negative electrode and a lithium iron phosphate positive electrode; a combination of a silicon-carbon negative electrode and a ternary positive electrode; a combination of a silicon-carbon negative electrode and a lithium cobalt oxide positive electrode; and a combination of a silicon-carbon negative electrode and a lithium manganese oxide positive electrode. Combinations such as a silicon anode and lithium iron phosphate cathode, a silicon anode and a ternary cathode, a silicon anode and a lithium cobalt oxide cathode, and a silicon anode and a lithium manganese oxide cathode can be listed, and in these cases the capacity of the battery system decreases after many cycles, but the method of pre-intercalating lithium with the electrolyte of the present invention can extend the life of lithium-ion batteries by 15 to 30 times. By replenishing lithium in the battery system via the electrolyte using the pre-intercalating agent having the above-described organic sulfinate structure of the present invention, it is possible to regenerate discarded lithium batteries on-site without disassembly, which is a significant improvement over conventional technology in terms of ease of handling, environmental protection, and cost.

[0050] In addition, the pre-intercalating agent having the above-described organic sulfinate structure of the present invention has sufficiently high specific energy and volumetric energy density, making it applicable to electrode materials with low initial efficiency, such as silicon monoxide (SiO), silicon-carbon, silicon, and black phosphorus. Although these electrode materials with low initial efficiency have high specific energy, stable cycle life, and low cost, their initial Coulomb rate is lower than the 92% required for lithium batteries, making them impractical for actual use. However, by applying the pre-intercalating agent having the above-described organic sulfinate structure of the present invention, it has been successful to realize batteries with high energy density. Furthermore, the SiO material itself is stable against water and oxygen, and compared to conventional commercial graphite anodes, its stability and energy density are significantly increased, while its cost is significantly reduced. Preferably, the positive electrode material to be combined with electrode materials with low initial efficiency such as silicon monoxide (SiO) is NCM811, a combination of a silicon-carbon negative electrode and a ternary positive electrode, a combination of a silicon-carbon negative electrode and a lithium iron phosphate positive electrode, a combination of a silicon-carbon negative electrode and a lithium cobalt oxide positive electrode, a combination of a silicon-carbon negative electrode and a lithium manganese oxide positive electrode, a combination of a silicon negative electrode and a ternary positive electrode, a combination of a silicon negative electrode and a lithium iron phosphate positive electrode, a combination of a silicon negative electrode and a lithium cobalt oxide positive electrode, and silicon The following combinations can be listed: a negative electrode and a lithium manganese oxide positive electrode; a black phosphorus negative electrode and a ternary positive electrode; a black phosphorus negative electrode and a lithium iron phosphate positive electrode; a black phosphorus negative electrode and a lithium cobalt oxide positive electrode; a black phosphorus negative electrode and a lithium manganese oxide positive electrode; a silicon monoxide negative electrode and a ternary positive electrode; a silicon monoxide negative electrode and a lithium iron phosphate positive electrode; a silicon monoxide negative electrode and a lithium cobalt oxide positive electrode; and a silicon monoxide negative electrode and a lithium manganese oxide positive electrode.

[0051] Furthermore, the pre-intercalating agent having the above-described organic sulfinate structure of the present invention has sufficiently high specific energy and volumetric energy density, and is therefore particularly applicable to battery systems in which neither the positive nor negative electrode contains lithium. Such electrode combinations include: a combination of graphite, a lithium-free negative electrode material, and sulfur-modified polyacrylonitrile (SPAN), a lithium-free positive electrode material; a combination of graphite, a lithium-free negative electrode material, and titanium disulfide as the positive electrode; a combination of graphite, a lithium-free negative electrode material, and vanadium pentoxide as the positive electrode; a combination of silicon-carbon negative electrode and sulfur-modified polyacrylonitrile, a lithium-free positive electrode material; a combination of silicon-carbon negative electrode and titanium disulfide as the positive electrode; a combination of graphite, a silicon-carbon negative electrode, and vanadium pentoxide as the positive electrode; a combination of silicon negative electrode and sulfur-modified polyacrylonitrile, a lithium-free positive electrode material; a combination of silicon negative electrode and titanium disulfide as the positive electrode; and a combination of graphite, a silicon negative electrode, and vanadium pentoxide as the positive electrode. By applying the above-mentioned pre-intercalating agent of the present invention, the energy density is 360 Wh kg -1 It reaches a level higher than current lithium-ion batteries (for example, 200-300 Wh / kg for lithium iron phosphate, lithium cobalt oxide, and ternary raw material systems). -1 Furthermore, even after 350 charge-discharge cycles, its capacity retention rate remains above 80%.

[0052] The lithium-free raw materials SPAN and graphite themselves are stable against water and oxygen, and their stability and ease of processing are significantly improved compared to conventional commercial lithium-containing cathode raw materials (e.g., lithium iron phosphate, lithium cobalt oxide, and ternary raw materials). SPAN, a lithium-free cathode raw material, is an organic polymer raw material, and its preparation process does not require the use of transition metals. Compared to conventional commercial lithium-containing cathode raw materials (e.g., lithium iron phosphate, lithium cobalt oxide, and ternary raw materials), it has higher recyclability, lower production and recovery costs, and is more environmentally friendly. The process of synthesizing the lithium-preintercalating raw material does not require conditions such as high temperature and high pressure, resulting in high stability and low production and storage costs.

[0053] [Electrode of Sodium Ion Secondary Battery] The electrode of the sodium ion secondary battery of the present invention can be obtained by the same method as the electrode of the lithium ion secondary battery described above, and the electrode raw material can be the raw material that can be used for the electrode of the sodium ion secondary battery among the electrodes of the lithium ion secondary battery described above. For example, the electrode combination is classified by the raw material of the sodium positive electrode, and polyanion-sodium electrochemical system (XO4) n- Or (X m O 3m+1 ) n- (X = B, S, P, Si, As, Mo, W), layered oxide-sodium electrochemical system Na x MO2 (x = 0~1, M = Fe, Mn, Ni, Co, Cr) and their combinations, Prussian blue-sodium electrochemical system {Na x M1[M2(CN)6] 1-y ·□ y ·nH2O (0 x 2, 0 y<1), M1 and M2 are different coordination transition metal ions such as Mn, Fe, Co, Ni, Cu, Zn, Cr, etc. (M1 coordinates to N, and M2 coordinates to C), and □ is the vacancy of [M2(CN)6]} and other sodium battery systems can be listed. Regarding conductive carbon, Super P, acetylene black, etc. can be listed. Regarding the binder, PVDF, PTFE, carbon nanotubes, etc. can be listed.

[0054] From the perspective that the stability of the sodium positive electrode raw material in the air is better, the synthesis cost and the difficulty of industrial technology are lower, and it is more suitable for large-scale production, as the positive electrode raw material, more preferably P2-type layered oxide (Na 2 / 3 M x N y O2, x + y = 1, M, N = Fe, Mn, Ni, Co, Cr), and regarding the negative electrode raw material combined with the positive electrode raw material, preferably hard carbon can be mentioned. Also, P2-type layered oxide lacking sodium (Na 0.67 Mn 0.67 Ni 0.33The O2 raw material itself is stable against water, oxygen, etc., and its stability is significantly higher compared to conventional commercial sodium-rich cathode raw materials, resulting in a significant reduction in cost.

[0055] Examples of hard carbon include resin carbon and organic polymer pyrolite carbon, which are commonly used raw materials in this field. Raw materials for hard carbon anode precursors include biomass, resin matrix, and bituminous.

[0056] [Electrolyte] As the lithium-ion electrolyte, an electrolyte prepared by dissolving the pre-intercalating agent having the above-described structure of lithium organosulfinate in the present invention in an organic solvent is used. In addition, it is necessary to use an electrolyte prepared by dissolving other lithium salts in an organic solvent. Examples of lithium salts include LiClO4, LiPF6, LiAsF6, LiSbF6, LiBF4, LiSO3F, LiCF3SO3, LiN(SO2CF3)2, LiTFSI, LiN(SO2C2F5)2, LiN(SO2CF3)(COCF3), Li(C4F9SO3), LiC(SO2CF3)3, LiBOB, lithium lower aliphatic carboxylate salts, LiAlCl4, etc. These may be used individually or as a mixture of two or more.

[0057] Examples of organic solvents that can be used include carbonate esters such as propylene carbonate, ethylene carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), 4-trifluoromethyl-1,3-dioxolan-2-one, and 1,2-di(methoxycarbonyloxy)ethane; ethers such as 1,3-dioxolane (DOL), 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyldifluoromethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran; esters such as methyl formate, methyl acetate, and γ-butyrolactone; nitriles such as acetonitrile and butyronitrile; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; urethanes such as 3-methyl-2-oxazolidinone; and sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 1,3-propanesultone.

[0058] As the sodium ion electrolyte, for example, an electrolyte prepared by dissolving the pre-intercalating agent having the above-described structure of organic sodium sulfinate in an organic solvent can be used. Examples of electrolytes include the above-described electrolytes of carbonate esters, sulfones, ethers, nitriles, etc.

[0059] The electrolyte is selected based on the battery system, and preferred electrolytes in this invention are carbonate ester electrolytes or ether electrolytes. When calculated using the molar ratio (mol / L) of the lithium salt in the electrolyte to the volume of the solvent, possible combinations include 1.0M NaClO4 (EC:DEC=1:1), 1.0M LiClO4 (EC:EMC=3:7), 1.0M LiPF6 (EC:EMC=3:7) + 1%LiClO4, 0.5M LiBOB + 0.5M LiTFSI (EC:EMC=3:7), 1.0M LiPF6 (DOL:DME=1:1) + 1%LiClO4, and the like.

[0060] [Pre-assemble the battery and rechargeable battery] The pre-assembled battery of the present invention is obtained by pre-sealing it using the lithium / sodium pre-intercalating electrode of the present invention described above. By charging the pre-sealed battery described above, it undergoes chemical conversion and the pre-intercalation of lithium / sodium is completed, and then it is sealed again to obtain the secondary battery of the present invention.

[0061] The present invention is by no means limited to the embodiments described above, and various modifications can be made within the scope of the claims. Embodiments obtained by appropriately combining the disclosed technical means in various embodiments are also included within the technical scope of the present invention. [Examples]

[0062] The present invention will be described in detail based on examples, but the present invention is by no means limited thereto.

[0063] Example 1 200 mmol of commercially available sodium trifluoromethanesulfinate was taken and added to 500 ml of ethyl acetate, and recrystallized. The resulting solid powder was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to obtain sodium trifluoromethanesulfinate, which is the raw material for pre-intercalating sodium. The aforementioned raw material for pre-intercalating sodium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0064] 100 mmol of sodium trifluoromethanesulfinate was added to 50 ml of acetonitrile and stirred evenly. 10 ml of concentrated hydrochloric acid was slowly added dropwise, and a white precipitate formed. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the precipitate was removed by filtration, and the precipitate was washed three times with ethyl acetate. The filtrate was collected, dried with anhydrous sodium sulfate, and the solvent was removed to obtain trifluoromethanesulfinic acid.

[0065] The obtained trifluoromethanesulfinic acid was dissolved in 80 ml of water and stirred thoroughly. Then, 90 mmol of lithium hydroxide was added at 0°C, and the temperature was slowly raised to room temperature and the reaction was allowed to proceed for 1 hour. After the reaction was complete, all the solvent was removed to obtain a white solid. An appropriate amount of ethyl acetate was added to the system to dissolve the solid, and then dichloromethane was added dropwise to the system until no more precipitate formed. The mixture was filtered to obtain a white solid. The same method was used to recrystallize the mixture three times. The resulting solids were left in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to finally obtain lithium trifluoromethanesulfinate, which is a raw material for pre-intercalating lithium. The aforementioned raw material for pre-intercalating lithium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0066] Battery manufacturing and measurement 50 mg of sodium trifluoromethanesulfinate was added to 1 g of sodium battery electrolyte (1.0 mol NaClO4EC:DEC=1:1), stirred, and dissolved to obtain a sodium battery electrolyte with pre-intercalated sodium properties. Carbon paper was used as the positive electrode. The positive electrode shell, carbon paper, diaphragm, sodium negative electrode, gasket, battery connector, and negative electrode shell were sequentially placed in a glove box, the electrolyte was added, and the components were fixed using a battery press to assemble a button cell. As shown in Figure 1a, the CV curve of a well-assembled button cell was measured using an electrochemical workstation with a sweep range of 2.5 to 4.0 V and a sweep speed of 0.1 mV / s. From the CV curve, it can be seen that sodium trifluoromethanesulfinate has irreversible sodium desorption capacity. As shown in Figure 1b, the desorption capacity of sodium trifluoromethanesulfinate was measured using a test channel of a button cell, employing constant current charging and discharging with a current of 0.06 mA and a cutoff voltage of 2.5 to 4.0 V. From the charge-discharge curve, it can be seen that sodium trifluoromethanesulfinate has a capacity close to 170 mAh / g, and its decomposition potential is between 3.6 and 3.7 V, indicating that it has an appropriate desodium potential and meets the basic requirements for a raw material that pre-intercalates sodium.

[0067] Figure 1a shows the CV curve test of a button-type battery containing sodium trifluoromethanesulfinate in this embodiment, where it can be seen that sodium trifluoromethanesulfinate begins to decompose at 3.7V, releasing sodium ions. Figure 1b shows the charge-discharge test of a button-type battery containing sodium trifluoromethanesulfinate in this embodiment, where it can be seen that sodium trifluoromethanesulfinate begins to decompose at 3.7V and has a capacity close to 170mAh / g.

[0068] 50 mg of lithium trifluoromethanesulfinate was added to 1 g of lithium battery electrolyte (1.0 mol LiClO4EC:EMC=3:7), stirred, and dissolved to obtain a lithium battery electrolyte with pre-intercalated lithium properties. Carbon paper was used as the positive electrode. The positive electrode shell, carbon paper, diaphragm, lithium negative electrode, gasket, battery connector, and negative electrode shell were sequentially placed in a glove box, the electrolyte was added, and the components were fixed using a battery press to assemble a button cell. As shown in Figure 2a, the CV curve of a well-assembled button cell was measured using an electrochemical workstation with a sweep range of 2.75 to 4.4 V and a sweep speed of 0.1 mV / s. From the CV curve, it can be seen that lithium trifluoromethanesulfinate has irreversible lithium desorption capacity. As shown in Figure 2b, the delithiation capacity of lithium trifluoromethanesulfinate was measured using a test channel of a button cell, employing constant current charging and discharging with a current of 0.06 mA and a cutoff voltage of 2.75 to 4.3 V. From the charge-discharge curves, it can be seen that lithium trifluoromethanesulfinate has a capacity close to 190 mAh / g, and its decomposition potential is between 3.8 and 3.9 V, indicating that it has an appropriate delithiation potential and meets the basic requirements for a lithium pre-intercalating material.

[0069] Figure 2a shows the CV curve test of the lithium trifluoromethanesulfinate button cell in this embodiment, where it can be seen that the lithium trifluoromethanesulfinate begins to decompose at 3.8V and releases lithium ions. Figure 2b shows the charge-discharge test of the lithium trifluoromethanesulfinate button cell in this embodiment, where it can be seen that the lithium trifluoromethanesulfinate begins to decompose at 3.8V and has a capacity close to 190mAh / g.

[0070] Figure 3 shows in-situ Raman measurements of a method in which lithium trifluoromethanesulfinate electrolyte pre-intercalates lithium in an embodiment of the present invention. It can be seen that the Raman characteristic peak of lithium trifluoromethanesulfinate gradually disappears as charging progresses, clearly indicating that lithium trifluoromethanesulfinate in the electrolyte gradually decomposes and releases lithium ions. Figure 3b shows a comparison of Raman spectroscopy in this embodiment for lithium trifluoromethanesulfinate powder, pure electrolyte, lithium trifluoromethanesulfinate dissolved in pure electrolyte, and after charging. It can be seen that the Raman characteristic peak of lithium trifluoromethanesulfinate disappears after charging, and at this time the characteristic peak of the electrolyte basically coincides with the Raman characteristic peak of the pure electrolyte. This clearly indicates that lithium trifluoromethanesulfinate completely disappears in the electrolyte after charging, and that the process of charging and pre-intercalating lithium has no fundamental effect on the electrolyte system.

[0071] Figure 4 shows a comparison of Raman spectroscopy of a newly prepared sample and a sample stored in dry air of lithium trifluoromethanesulfinate electrolyte in an embodiment of the present invention. The Raman characteristic peaks of the newly prepared sample and the sample stored in dry air are basically identical, indicating that the raw material for pre-intercalating lithium has relatively good chemical stability.

[0072] Example 2 200 mmol of commercially available sodium methanesulfinate was taken and placed in water, recrystallized, and the resulting solid powder was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to obtain sodium methanesulfinate, which is the raw material for pre-intercalating sodium. The aforementioned raw material for pre-intercalating sodium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0073] 100 mmol of sodium methanesulfinate was added to 50 ml of acetonitrile and stirred evenly. 10 ml of concentrated hydrochloric acid was slowly added dropwise, and a white precipitate formed. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the precipitate was removed by filtration, and the precipitate was washed three times with ethyl acetate. The filtrate was collected, dried with anhydrous sodium sulfate, and the solvent was removed to obtain methanesulfinic acid.

[0074] The obtained methanesulfinic acid was dissolved in 80 ml of water and stirred thoroughly. Then, 90 mmol of lithium hydroxide was added at 0°C, and the temperature was slowly raised to room temperature and the reaction was allowed to proceed for 1 hour. After the reaction was complete, all the solvent was removed to obtain a white solid, which was washed three times with ethanol. The obtained solid was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to finally obtain lithium methanesulfinate, which is a raw material for pre-intercalating lithium. The aforementioned raw material for pre-intercalating lithium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0075] Battery manufacturing and measurement 100 mg of sodium methanesulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the container was placed in a vacuum dryer and vacuum-dried at 60-70°C for 10 hours to obtain a sodium methanesulfinate electrode section, which was then cut into a Φ12 circular section. The positive electrode shell, sodium methanesulfinate electrode section, diaphragm, sodium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5a, the desorption capacity of sodium methanesulfinate was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.5-4.0 V. From the charge-discharge curve, it can be seen that sodium methanesulfinate has a capacity close to 262 mAh / g, and its decomposition potential is between 3.2 and 3.3 V, indicating that it has an appropriate desodium potential and meets the basic requirements for a raw material that pre-intercalates sodium.

[0076] Figure 5a shows a charge-discharge test of a button-type battery containing sodium methanesulfinate in this embodiment. It can be seen that the sodium methanesulfinate begins to charge and decompose at 3.2V and has a capacity close to 262mAh / g. The raw material for pre-intercalating sodium has an appropriate desodium potential and clearly meets the basic requirements for a raw material for pre-intercalating sodium.

[0077] 100 mg of lithium methanesulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the mixture was vacuum-dried in a vacuum dryer at 60-70°C for 10 hours to obtain lithium methanesulfinate electrode sections. These electrode sections were cut into Φ12 circular sections. The positive electrode shell, lithium methanesulfinate electrode section, diaphragm, lithium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5b, the desorption capacity of lithium methanesulfinate was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.75-4.3 V. From the charge-discharge curve, it can be seen that lithium methanesulfinate has a capacity close to 310 mAh / g, and its decomposition potential is between 3.7 and 3.8 V, indicating that it has an appropriate delithiation potential and meets the basic requirements for a raw material that pre-intercalates lithium.

[0078] Figure 5 shows the charge-discharge test of the lithium methanesulfinate button cell in this embodiment, and it can be seen that the lithium methanesulfinate begins to charge and decompose at 3.7V and has a capacity close to 311mAh / g. It is clear that the lithium pre-intercalation material has an appropriate delithiation potential and satisfies the basic requirements for lithium pre-intercalation material.

[0079] Example 3 200 mmol of commercially available sodium ethanesulfinate was taken and placed in water, recrystallized, and the resulting solid powder was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to obtain sodium ethanesulfinate, which is the raw material for pre-intercalating sodium. The said raw material for pre-intercalating sodium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0080] 100 mmol of sodium ethanesulfinate was added to 50 ml of acetonitrile and stirred evenly. 10 ml of concentrated hydrochloric acid was slowly added dropwise, and a white precipitate formed. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the precipitate was removed by filtration, and the precipitate was washed three times with ethyl acetate. The filtrate was collected, dried with anhydrous sodium sulfate, and the solvent was removed to obtain ethanesulfinic acid.

[0081] The obtained methanesulfinic acid was dissolved in 80 ml of water and stirred thoroughly. Then, 90 mmol of lithium hydroxide was added at 0°C, and the temperature was slowly raised to room temperature and the reaction was allowed to proceed for 1 hour. After the reaction was complete, all the solvent was removed to obtain a white solid, which was washed three times with ethanol. The obtained solid was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to finally obtain lithium ethanesulfinate, which is a raw material for pre-intercalating lithium. The aforementioned raw material for pre-intercalating lithium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0082] Battery manufacturing and measurement 100 mg of sodium ethanesulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the mixture was vacuum-dried in a vacuum dryer at 60-70°C for 10 hours to obtain sodium ethanesulfinate electrode sections, which were then cut into Φ12 circular sections. The positive electrode shell, sodium ethanesulfinate electrode sections, diaphragm, sodium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5a, the desorption capacity of sodium ethanesulfinate was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.5-4.0 V. From the charge-discharge curve, it can be seen that sodium ethanesulfinate has a capacity close to 230 mAh / g, and its decomposition potential is between 3.2 and 3.3 V, indicating that it has an appropriate desodiumization potential and meets the basic requirements for a raw material that pre-intercalates sodium.

[0083] Figure 5a shows the charge-discharge test of a button-type battery containing sodium ethanesulfinate in this embodiment. It can be seen that the sodium ethanesulfinate begins to charge and decompose at 3.1V and has a capacity close to 230mAh / g. The raw material for pre-intercalating sodium has an appropriate desodium potential and clearly meets the basic requirements for a raw material for pre-intercalating sodium.

[0084] 100 mg of lithium ethanesulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the container was placed in a vacuum dryer and vacuum-dried at 60-70°C for 10 hours to obtain lithium ethanesulfinate electrode sections, which were then cut into Φ12 circular sections. The positive electrode shell, lithium ethanesulfinate electrode sections, diaphragm, lithium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5b, the desorption capacity of lithium ethanesulfinate was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.75-4.3 V. From the charge-discharge curve, it can be seen that lithium ethanesulfinate has a capacity close to 265 mAh / g, and its decomposition potential is between 3.8 and 3.9 V, indicating that it has an appropriate delithiation potential and meets the basic requirements for a raw material that pre-intercalates lithium.

[0085] Figure 5b shows the charge-discharge test of the lithium ethanesulfinate button cell in this embodiment, and it can be seen that the lithium ethanesulfinate begins to charge and decompose at 3.8V and has a capacity close to 265mAh / g. It is clear that the lithium pre-intercalating material has an appropriate delithiation potential and satisfies the basic requirements for lithium pre-intercalating materials.

[0086] Example 4 Commercially available sodium phenylsulfinate was taken at a concentration of 200 mmol, placed in water, and recrystallized. The resulting solid powder was placed in a vacuum dryer and vacuum-dried at 60-70°C for 10 hours to obtain sodium phenylsulfinate, which is the raw material for pre-intercalating sodium. The aforementioned raw material for pre-intercalating sodium is stable in dry air, can still be used normally even after moisture absorption and drying, and possesses good chemical stability.

[0087] 100 mmol of sodium phenylsulfinate was added to 50 ml of acetonitrile and stirred evenly. 10 ml of concentrated hydrochloric acid was slowly added dropwise, and a white precipitate formed. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the precipitate was removed by filtration, and the precipitate was washed three times with ethyl acetate. The filtrate was collected, dried with anhydrous sodium sulfate, and the solvent was removed to obtain phenylsulfinic acid.

[0088] The obtained phenylsulfinic acid was dissolved in 80 ml of water and stirred thoroughly. Then, 90 mmol of lithium hydroxide was added at 0°C, and the temperature was slowly raised to room temperature and the reaction was allowed to proceed for 1 hour. After the reaction was complete, all the solvent was removed to obtain a white solid, which was washed three times with ethanol. The obtained solid was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to finally obtain lithium phenylsulfinate, which is a raw material for pre-intercalating lithium. The aforementioned raw material for pre-intercalating lithium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0089] Battery manufacturing and measurement 100 mg of sodium phenylsulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the mixture was vacuum-dried in a vacuum dryer at 60-70°C for 10 hours to obtain sodium phenylsulfinate electrode sections, which were then cut into Φ12 circular sections. The positive electrode shell, sodium phenylsulfinate electrode sections, diaphragm, sodium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5a, the desorption capacity of sodium phenylsulfinate was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.5-4.0 V. From the charge-discharge curve, it can be seen that sodium phenylsulfinate has a capacity close to 163 mAh / g, and its decomposition potential is between 3.3 and 3.4 V, indicating that it has an appropriate desodium potential and meets the basic requirements for a raw material that pre-intercalates sodium.

[0090] Figure 5a shows the charge-discharge test of a button-type battery containing sodium phenylsulfinate in this embodiment. It can be seen that the sodium phenylsulfinate begins to charge and decompose at 3.3V and has a capacity close to 163mAh / g. The raw material for pre-intercalating sodium has an appropriate desodium potential and clearly meets the basic requirements for a raw material for pre-intercalating sodium.

[0091] 100 mg of lithium phenylsulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the mixture was vacuum-dried in a vacuum dryer at 60-70°C for 10 hours to obtain lithium phenylsulfinate electrode sections. These electrode sections were cut into Φ12 circular sections. The positive electrode shell, lithium phenylsulfinate electrode section, diaphragm, lithium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5b, the desorption capacity of lithium phenylsulfinate was measured using a test channel of the button cell, employing constant current charging and discharging at a current of 0.06 mA and a cutoff voltage of 2.75-4.3 V. From the charge-discharge curve, it can be seen that lithium phenylsulfinate has a capacity close to 180 mAh / g, and its decomposition potential is between 3.9 and 4.0 V, indicating that it has an appropriate delithiation potential and meets the basic requirements for a raw material for pre-intercalating lithium.

[0092] Figure 5b shows the charge-discharge test of the lithium phenylsulfinate button cell in this embodiment, and it can be seen that the lithium phenylsulfinate begins to charge-decompose at 3.9V and has a capacity close to 181mAh / g. It is clear that the lithium pre-intercalation material has an appropriate delithiation potential and satisfies the basic requirements for lithium pre-intercalation material.

[0093] Example 5 Commercially available sodium p-toluenesulfinate was taken at a concentration of 200 mmol, placed in water, and recrystallized. The resulting solid powder was placed in a vacuum dryer and vacuum-dried at 60-70°C for 10 hours to obtain sodium p-toluenesulfinate, which is the raw material for pre-intercalating sodium. The aforementioned raw material for pre-intercalating sodium is stable in dry air, can still be used normally even after moisture absorption and drying, and possesses good chemical stability.

[0094] 100 mmol of sodium p-toluenesulfinate was added to 50 ml of acetonitrile and stirred evenly. 10 ml of concentrated hydrochloric acid was slowly added dropwise, and a white precipitate formed. After the addition was complete, the mixture was stirred at room temperature for 2 hours. After the reaction was complete, the precipitate was removed by filtration, and the precipitate was washed three times with ethyl acetate. The filtrate was collected, dried with anhydrous sodium sulfate, and the solvent was removed to obtain p-toluenesulfinic acid.

[0095] The obtained p-toluenesulfinic acid was dissolved in 80 ml of water and stirred thoroughly. Then, 90 mmol of lithium hydroxide was added at 0°C, and the temperature was slowly raised to room temperature and the reaction was allowed to proceed for 1 hour. After the reaction was complete, all the solvent was removed to obtain a white solid, which was washed three times with ethanol. The obtained solid was placed in a vacuum dryer and vacuum dried at 60-70°C for 10 hours to finally obtain lithium p-toluenesulfinate, a raw material for pre-intercalating lithium. The aforementioned raw material for pre-intercalating lithium is stable in dry air, can still be used normally even after moisture absorption and drying, and has good chemical stability.

[0096] Battery manufacturing and measurement 100 mg of p-toluenesulfinate sodium, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the container was placed in a vacuum dryer and vacuum-dried at 60-70°C for 10 hours to obtain p-toluenesulfinate sodium electrode sections, which were then cut into Φ12 circular sections. The positive electrode shell, p-toluenesulfinate sodium electrode sections, diaphragm, sodium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5a, the desorption capacity of p-toluenesulfinate sodium was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.5-4.0 V. From the charge-discharge curve, it can be seen that p-toluenesulfinate sodium has a capacity close to 150 mAh / g, and its decomposition potential is between 3.3 and 3.4 V, indicating that it has an appropriate desodiumization potential and meets the basic requirements for a raw material that pre-intercalates sodium.

[0097] Figure 5a shows the charge-discharge test of a button-type battery containing p-toluenesulfinate sodium in this embodiment. It can be seen that the p-toluenesulfinate sodium begins to charge and decompose at 3.3V and has a capacity close to 150mAh / g. The raw material for pre-intercalating sodium has an appropriate desodium potential and clearly meets the basic requirements for a raw material for pre-intercalating sodium.

[0098] 100 mg of lithium p-toluenesulfinate, 80 mg of Super P, 400 mg of PVDF solution (dissolved in 5% NMP), and an appropriate amount of NMP were added to a ball mill container and homogenized using an agate ball mill. A 200 nanometer film was blade-coated onto aluminum foil using a coating machine, and the mixture was vacuum-dried in a vacuum dryer at 60-70°C for 10 hours to obtain a lithium p-toluenesulfinate electrode section. The electrode section was cut into a Φ12 circular section. The positive electrode shell, lithium p-toluenesulfinate electrode section, diaphragm, lithium section negative electrode, gasket, battery connector, and negative electrode shell were sequentially installed in a glove box and fixed using a battery press to assemble a button cell. As shown in Figure 5b, the desorption capacity of lithium p-toluenesulfinate was measured using a test channel of the button cell with constant current charging and discharging, at a current of 0.06 mA and a cutoff voltage of 2.75-4.3 V. From the charge-discharge curve, it can be seen that lithium p-toluenesulfinate has a capacity close to 165 mAh / g, and its decomposition potential is between 3.9 and 4.0 V, indicating that it has an appropriate delithiation potential and meets the basic requirements for a raw material that pre-intercalates lithium.

[0099] Figure 5b shows the charge-discharge test of a button-type battery containing lithium p-toluenesulfinate in this embodiment. It can be seen that the lithium p-toluenesulfinate begins to charge and decompose at 3.9V and has a capacity close to 165mAh / g. The material used to pre-intercalate lithium has an appropriate delithiation potential and clearly meets the basic requirements for a material used to pre-intercalate lithium.

[0100] Example 6 Aside from substituting the sodium methanesulfinate in Example 2 with commercially available sodium p-chlorophenylsulfinate, sodium p-chlorophenylsulfinate and lithium p-chlorophenylsulfinate, which are pre-intercalating raw materials for lithium, can be produced in a manner otherwise identical to that of Example 2. The aforementioned pre-intercalating raw materials for lithium are stable in dry air, can still be used normally even after being dried after absorbing moisture, and possess good chemical stability.

[0101] Battery manufacturing and measurement A battery was manufactured and measured using the same method as in Example 2. The desorption capacity of sodium p-chlorophenylsulfinate was measured using a test channel of a button-type battery with constant current charging and discharging at a current of 0.06 mA and a cutoff voltage of 2.5 to 4.0 V. It was determined that sodium p-chlorophenylsulfinate had a capacity close to 135 mAh / g, and its decomposition potential was between 3.3 and 3.4 V, indicating an appropriate desodium potential and meeting the basic requirements for a raw material that pre-intercalates sodium. Similarly, the desorption capacity of lithium p-chlorophenylsulfinate was measured using a test channel of a button-type battery with constant current charging and discharging at a current of 0.06 mA and a cutoff voltage of 2.75 to 4.3 V. It was determined that lithium p-chlorophenylsulfinate had a capacity close to 147 mAh / g, and its decomposition potential was between 3.9 and 4.0 V, indicating an appropriate delithiation potential and meeting the basic requirements for a raw material that pre-intercalates lithium.

[0102] Example 7 Aside from substituting the sodium methanesulfinate in Example 2 with commercially available sodium tetrahydropyran-4-sulfinate, sodium tetrahydropyran-4-sulfinate and lithium tetrahydropyran-4-sulfinate, which are pre-intercalating raw materials for lithium, can be produced in a manner otherwise identical to that of Example 2. The aforementioned pre-intercalating raw materials for lithium are stable in dry air, can still be used normally even after being dried after absorbing moisture, and possess good chemical stability.

[0103] Battery manufacturing and measurement A battery was manufactured and measured using the same method as in Example 2. The desorption capacity of sodium tetrahydropyran-4-sulfinate was measured using a test channel of a button-type battery with constant current charging and discharging at a current of 0.06 mA and a cutoff voltage of 2.5 to 4.0 V. It was determined that sodium tetrahydropyran-4-sulfinate had a capacity close to 157 mAh / g, and its decomposition potential was between 3.3 and 3.4 V, indicating an appropriate desodium potential and meeting the basic requirements for a raw material that pre-intercalates sodium. Similarly, the desorption capacity of lithium tetrahydropyran-4-sulfinate was measured using a test channel of a button-type battery with constant current charging and discharging at a current of 0.06 mA and a cutoff voltage of 2.75 to 4.3 V. It was determined that lithium tetrahydropyran-4-sulfinate had a capacity close to 173 mAh / g, and its decomposition potential was between 3.9 and 4.0 V, indicating an appropriate delithiation potential and meeting the basic requirements for a raw material that pre-intercalates lithium.

[0104] Example 8 A system combining sulfur-modified polyacrylonitrile SPAN, a lithium-free raw material, and graphite was adopted. 2 wt% lithium trifluoromethanesulfinate was dissolved in the electrolyte to construct a lithium-free pouch-type battery with a capacity of approximately 28.6 Ah.

[0105] For the graphite, commercially available graphite raw material (Sigma-Aldrich) was used, and for the sulfur-modified polyacrylonitrile, a self-scalding raw material was used, with elemental analysis results showing a sulfur content of 39.5%, a carbon content of 40.58%, a nitrogen content of 15.05%, and a hydrogen content of 0.59%.

[0106] Conductive carbon, sulfur-modified polyacrylonitrile, and PVDF were added to an appropriate amount of NMP in a ratio of 90:5:5 and thoroughly mixed. This mixture was then evenly coated onto aluminum foil using a blade, dried, and cut to obtain a positive electrode section. Graphite, PVDF, and NMP were added to an appropriate amount of NMP in a ratio of 92:4:4 and thoroughly mixed. This mixture was then evenly coated onto copper foil using a blade, dried, and cut to obtain a negative electrode section. A pouch-type battery with approximately 28.6 Ah of lithium-free capacity was constructed by stacking these sections in multiple layers, and lithium replenishment of the battery system was achieved through charging.

[0107] As shown in Figure 7, its energy density is 360 Wh kg -1 It reached a Coulomb efficiency of 99.7% on its first use, and after 350 charge-discharge cycles, its capacity retention rate was still above 80%.

[0108] Example 9 The cathode raw material is NCM811 (LiNi 0.8 Mn 0.1 Co 0.1 A system combining O2 and SiO was adopted, and 2 wt% lithium trifluoromethanesulfinate was dissolved in the electrolyte to construct a lithium-free pouch-type lithium battery with a capacity of approximately 14 Ah.

[0109] SiO, conductive carbon (Super P), polyacrylic acid (PAA), and carbon nanotubes were added to an appropriate amount of NMP in a ratio of 80:10:4:6 and mixed evenly. The mixture was then coated onto copper foil to produce a negative electrode, which was dried and cut to obtain a positive electrode section. NCM811, Super P, and PVDF were added to an appropriate amount of NMP in a ratio of 92:4:4 and mixed thoroughly. The mixture was then coated onto aluminum foil to produce a positive electrode, which was dried and cut to obtain a negative electrode section. With a negative-to-positive electrode capacity ratio of 1.01, a 14Ah dry cell was assembled, and lithium replenishment of the battery system was achieved by charging.

[0110] As shown in Figure 8, its energy density is 352 Wh kg -1 It reached a Coulomb efficiency of 99.7% on its first charge-discharge cycle, and after 800 charge-discharge cycles, its capacity retention rate remained above 87.6%.

[0111] Example 10 The cathode raw material is NCM811 (LiNi 0.8 Mn 0.1 Co 0.1 A system combining O2 and SiO was adopted, and 2 wt% lithium trifluoromethanesulfinate was dissolved in the electrolyte to construct a lithium-free pouch-type lithium battery with a capacity of approximately 3.0 Ah.

[0112] The electrode material load is 4.0 mAh cm⁻¹. -2The area capacity ratio between the negative and positive electrodes was 1.05, and charge-discharge tests were conducted under test conditions of a 0.5C multiplier. As shown in Figure 9, the initial efficiency of the pouch-type battery was 57% when no lithium replenishment material was added, but when the commercially available lithium replenishment agent LNC was added, the initial efficiency increased to 62% when the maximum amount added was 4% by mass fraction. As shown in Figure 9, in the present invention, the initial efficiency can be increased to 100% by replenishing lithium with the electrolyte, and compared to a battery system with no lithium replenishment material added but with the commercially available lithium replenishment agent LNC added, the initial efficiency of the battery is effectively increased, and its cycle stability is not affected, with a capacity retention rate of 90% or more after 800 stable cycles. It has become clear that the present invention has relatively good practicality compared to battery systems with low lithium content.

[0113] Example 11 Sodium trifluoromethanesulfinate was dissolved in an electrolyte at a concentration of 5 wt% to obtain a sodium battery electrolyte that has the ability to pre-intercalate sodium. A sodium battery dry cell was assembled, the sodium battery electrolyte was injected, and the battery system was charged to replenish sodium. As shown in Figure 10, in a sodium cathode-copper battery system, both the charge and discharge capacities increased significantly after sodium trifluoromethanesulfinate was added to the electrolyte.

[0114] Example 12 Sodium methanesulfinate was mixed at a ratio of 90 wt% with a fixed ratio of conductive carbon and a binder to obtain a sodium-replenished slurry. The slurry was evenly coated to a fixed thickness using a blade to cover the electrode section of the positive electrode, dried, assembled as a sodium battery, injected sodium battery electrolyte, and charged to realize that the battery system replenished sodium. As shown in Figure 11, in the sodium positive electrode-copper battery system, after the positive electrode surface was blade coated with sodium methanesulfinate, both the charge and discharge capacities increased significantly.

[0115] Example 13 Sodium methanesulfinate was mixed at a ratio of 5 wt% with a constant ratio of sodium battery positive electrode material, conductive carbon, and binder to obtain a sodium positive electrode slurry. The slurry was evenly blade-coated onto a current collector to a constant thickness, dried, assembled into a sodium battery dry cell, injected with sodium battery electrolyte, and charged to replenish sodium in the battery system. As shown in Figure 12, in the sodium positive electrode-copper battery system, after a constant ratio of sodium methanesulfinate was mixed into the positive electrode, both the charge and discharge capacities increased significantly.

[0116] Example 14 Sodium-poor P2 type layered oxide (Na 0.67 Mn 0.67 Ni 0.33 A system of O2 and graphite was used, and 5 wt% sodium trifluoromethanesulfinate was dissolved in the electrolyte to construct a pouch-type sodium battery with a capacity of approximately 1 Ah.

[0117] Na 0.67 Mn 0.67 Ni 0.33 O2, conductive carbon (Super P), and (PVDF) were added to an appropriate amount of NMP in a ratio of 80:10:10 and mixed evenly. The mixture was then applied to aluminum foil to produce a positive electrode, which was dried and cut to obtain an electrode section of the positive electrode. Hard carbon, Super P, and PVDF were added to an appropriate amount of NMP in a ratio of 92:4:4 and mixed evenly. The mixture was then applied to copper foil to produce a positive electrode. This was dried, cut, and assembled into a dry cell. With a negative-to-positive electrode capacity ratio of 1.1, a 1Ah dry cell was assembled, and sodium replenishment of the battery system was achieved through charging.

[0118] As shown in Figure 13, without sodium replenishment, the entire battery had an initial capacity of only 77 mAh / g. By using a method in which sodium is replenished with an electrolyte, an initial capacity of 96 mAh / g was achieved, which is a level that can be industrialized for all batteries with a sodium-rich positive electrode.

[0119] Example 15 A system consisting of a graphite negative electrode and a lithium iron phosphate positive electrode was used to construct a pouch-type lithium battery with a capacity of approximately 1 Ah.

[0120] Conductive carbon, lithium iron phosphate, and PVDF were added to an appropriate amount of NMP in a ratio of 90:5:5 and thoroughly mixed. This mixture was then evenly coated onto aluminum foil using a blade, dried, and cut to obtain a positive electrode section. Graphite, PVDF, and NMP were added to an appropriate amount of NMP in a ratio of 92:4:4 and thoroughly mixed. This mixture was then evenly coated onto copper foil using a blade, dried, and cut to obtain a negative electrode section. A pouch-type battery with a capacity of approximately 1 Ah was formed by stacking these sections in multiple layers. After 1800 charge-discharge cycles at 1C, the capacity decreased to 85%, resulting in a used battery.

[0121] The electrolyte was drained from the discarded battery under the condition that the overall structure of the battery was not destroyed. Lithium replenishment of the battery system was achieved by dissolving 2 wt% lithium trifluoromethanesulfinate in the electrolyte, injecting the electrolyte containing the lithium replenishment agent into the discarded battery, and then charging it.

[0122] As shown in Figure 14, after approximately 1800 cycles, the battery system capacity decreased to 85%. By replenishing lithium with the electrolyte described in this invention, the capacity was increased again to 99.6%. After another approximately 1800 cycles, the battery system capacity decreased again to 85%. By replenishing lithium with the electrolyte described in this invention, the capacity was increased again to 98.8%. Furthermore, after the third cycle and lithium replenishment of the electrolyte, the battery capacity was restored to 98.1%, and after 7717 cycles, the battery capacity retention rate reached 97.4%. Based on trend predictions, 30,000 to 60,000 battery cycles can be achieved.

[0123] Regarding the measurement method for initial Coulomb efficiency, under conditions where the battery is tested with constant current charge and discharge, the ratio of the initial discharge capacity to the initial charge capacity is the initial Coulomb efficiency.

[0124] Regarding the method for measuring the capacity retention rate after n charge-discharge cycles, under conditions where the battery is tested with constant current charge-discharge, the ratio of the discharge capacity after the nth cycle to the discharge capacity after the first cycle is the capacity retention rate after n charge-discharge cycles.

[0125] Regarding methods for measuring energy density, the product of the total capacity of the battery and the plateau value of the discharge voltage is the battery capacity, the ratio of the battery capacity to the battery mass is the critical energy density of the battery, and the ratio of the battery capacity to the battery mass is the volumetric energy density of the battery.

[0126] Measurements and calculations of the amount of pre-intercalating agent remaining in the electrodes in the above-described examples revealed that in all cases it was lower than 0.005 mmol. [Industrial applicability]

[0127] The present invention provides a pre-intercalating agent that does not leave any by-products in the battery after pre-intercalating lithium / sodium, has good stability, is advantageous in terms of safety during the lithium / sodium pre-intercalating process, has high energy density and capacity retention, a pre-intercalated lithium / sodium cathode, a lithium / sodium ion battery containing these, and a method for pre-intercalating lithium / sodium.

Claims

1. Formula (1) below 【Chemistry 1】 (In formula (1) above, R is selected from alkyl groups having 1 to 10 carbon atoms and halogen-substituted alkyl groups thereof, aryl groups having a benzene ring, a thiophene ring, a furan ring, a pyridine ring and halogen-substituted aryl groups thereof, chain ethers and cyclic ethers having 1 to 10 carbon atoms, chain esters and cyclic esters having 1 to 10 carbon atoms, and X represents Na or Li.) A preintercalating agent used to preintercalate lithium or sodium, characterized by having an organosulfinate structure as shown in [image / figure] as its backbone.

2. In the formula (1), R is an alkyl group such as -Me, -Et, -CF ３ , -C ２ F ５ , -C ４ F ９ , a halogen-substituted alkyl group such as -Ph, -CH ３ C ６ H ４ , -C ５ NH ４ , -C ４ H ３ S, -C ４ H ３ O, an aryl group such as -FC ６ H ４ , -ClC ６ H ４ The preintercalating agent according to claim 1, characterized in that it is selected from the above groups.

3. A pre-intercalated lithium positive electrode having a structure in which an active material layer containing a positive electrode active material, a conductive agent and a binder is formed on a current collector, wherein lithium is pre-intercalated using the pre-intercalating agent described in claim 1 or 2, and in formula (1), X represents Li, Based on a battery capacity of 1 Ah, the amount of pre-intercalating agent in the pre-intercalated lithium cathode before the lithium pre-intercalating process is n moles. [Math 1] (In the above equation, F is the Faraday constant, and c is the amount of lithium pre-intercalated for a battery capacity of 1 Ah, calculated by Ah.) A pre-intercalated lithium cathode characterized in that the content of the pre-intercalating agent in the pre-intercalated lithium cathode after the lithium pre-intercalation treatment is less than 0.005 mmol.

4. The pre-intercalated lithium cathode according to claim 3, characterized in that the cathode active material is selected from lithium iron phosphate, sulfur-modified polyacrylonitrile (SPAN), ternary raw materials, lithium cobaltate, lithium manganate, titanium disulfide, vanadium pentoxide, and Prussian blue.

5. A pre-assembled lithium-ion secondary battery characterized by having a pre-intercalated lithium positive electrode and a negative electrode as described in claim 3 or 4.

6. The provisional lithium-ion secondary battery according to claim 5, characterized in that the negative electrode is selected from graphite, lithium metal, silicon-carbon, silicon, a silicon-graphite composite, a silicon-lithium metal composite, a graphite-lithium metal composite, silicon monoxide, and black phosphorus.

7. A lithium-ion secondary battery according to claim 5 or 6, characterized in that it is obtained by performing a pre-intercalation process of the lithium.

8. A pre-intercalated sodium positive electrode having a structure in which an active material layer containing a positive electrode active material, a conductive agent and a binder is formed on a current collector, wherein sodium is pre-intercalated using the pre-intercalating agent described in claim 1 or 2, and in formula (1), X represents Na, Based on a battery capacity of 1 Ah, the amount of pre-intercalating agent in the pre-intercalated sodium cathode before the sodium pre-intercalating process is n moles. [Math 2] (In the above equation, F is the Faraday constant, and c is the amount of sodium pre-intercalated for a battery capacity of 1 Ah, calculated using Ah.) A pre-intercalated sodium cathode characterized in that the content of the pre-intercalating agent in the pre-intercalated sodium cathode after the sodium pre-intercalating treatment is less than 0.005 mmol.

9. The aforementioned positive electrode active material is Na ０．６７ Mn ０．６７ Ni ０．３３ O ２ P2-type layered oxide, Prussian blue, NaNi ０．３３ Fe ０．３３ Mn ０．３３ O ２ The pre-intercalated sodium cathode according to claim 8, characterized in that it is selected from an O3-type layered oxide represented by and sodium vanadium phosphate.

10. A pre-assembled sodium-ion secondary battery characterized by having a pre-intercalated sodium positive electrode as described in claim 8 or 9.

11. The provisionally assembled sodium-ion secondary battery according to claim 10, characterized in that the negative electrode is selected from soft carbon and hard carbon.

12. A sodium-ion secondary battery, characterized in that it is obtained by performing the process of pre-intercalating the sodium, as described in claim 10 or 11.

13. A method for pre-intercalating lithium or sodium, characterized by performing a pre-intercalating treatment using the pre-intercalating agent described in claim 1 or 2.

14. A method for pre-intercalating lithium or sodium according to claim 13, characterized in that the pre-intercalating agent is dissolved in an electrolyte to perform a pre-intercalating treatment of lithium or sodium.

15. A method for pre-intercalating lithium or sodium according to claim 14, characterized in that the pre-intercalating agent is dissolved in an electrolyte and the electrolyte is added to a used battery electrode to pre-intercalate the lithium or sodium.

16. A method for pre-intercalating lithium or sodium according to claim 14 or 15, characterized by dissolving the pre-intercalating agent in an electrolyte solution at a mass fraction of 0.1% to 30% and performing a pre-intercalating treatment of lithium or sodium.

17. A method for pre-intercalating lithium or sodium according to claim 13, characterized by doping the positive electrode with the pre-intercalating agent and performing a pre-intercalating treatment of the lithium or sodium.

18. A method for pre-intercalating lithium or sodium according to claim 13, characterized by coating the positive electrode with the pre-intercalating agent and performing a pre-intercalating treatment of lithium or sodium.

19. A method for pre-intercalating lithium or sodium according to any one of claims 13, 14, 15, 17, or 18, characterized in that the electrolyte used in the process of pre-intercalating lithium or sodium is an electrolyte of carbonate esters or an electrolyte of ethers.

20. The electrolyte of the aforementioned carbonate esters is NaClO ４ 1.0 mol, LiClO ４ 1.0mol, LiPF ６ 1.0mol+LiClO ４ The electrolyte is selected from 1%, LiBOB 0.5 mol + LiTFSI 0.5 mol, and the electrolyte of the esters is LiPF ６ 1.0mol+LiClO ４ A method for pre-intercalating lithium or sodium according to claim 19, characterized in that the concentration is 1%.

21. Step (1) of taking an organic sulfinate sodium salt having the structure of an organic sulfinate salt in formula (1) of claim 1 or 2 in which X represents Na, and recrystallizing it in a solvent to obtain a raw material for pre-intercalating sodium, Step (2) involves taking the raw material for pre-intercalating sodium in step (1) above, placing it in an organic solvent, adding an appropriate amount of acid dropwise, stirring to allow the reaction to occur, extracting and drying, and then evaporating and drying the solvent. Step (3) involves adding the product obtained in step (2) to deionized water, adding an appropriate amount of lithium salt, stirring to react, and evaporating the solvent, and Step (4): The solid obtained in step (3) is recrystallized using ethyl acetate and dichloromethane, and the resulting solid powder is dried to obtain a lithium organic sulfinate salt having the structure of an organic sulfinate in formula (1) of claim 1 or 2, where X is Li. A method for producing a preintercalating agent used for preintercalating lithium, characterized by containing [a specific compound / component].

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