Polymer-coated electrode active materials, their manufacture and use

Abstract

The present invention provides a coated particulate material comprising a plurality of core particles, each core particle having a formula (I), Li[Ni 1-x-y-z Co x Mn y M z ]O2, and the surface of a core particle exhibits a coating comprising at least one polycationic organic polymer or at least one polyanionic organic polymer.

Description

Detailed Description of the Invention

[0001] The present invention relates to polymer-coated electrode active materials, particularly NCM-based polymer-coated cathode active materials, used to improve the cycling stability of electrode active materials in electronic devices such as batteries. The present invention also relates to the manufacture and use of polymer-coated electrode active materials. A preferred use of the polymer-coated electrode active materials is as an electrode active material in lithium-ion batteries (lithium-ion electrochemical cells), most preferably as an electrode active material in solid-state lithium-ion batteries (also called solid-state lithium-ion electrochemical cells).

[0002] [explanation] [Background technology] High-nickel ternary cathode material LiNi 1-x-y Co x Mn yThiophosphate-based solid-state batteries (SSBs) containing O2 (NCM), particularly solid-state lithium-ion batteries or solid-state lithium-ion electrochemical cells, are promising next-generation energy storage technologies due to their expected high specific discharge capacity and improved safety. However, a serious problem to overcome for large-scale, high-energy density applications is the rapid capacity degradation during cell cycling. Typically, interphases and cracks form during NCM cycling, causing contact loss and an increase in the length of the lithium diffusion path. Herein, a uniform polymer coating is applied to NCMs by a spray-drying process. This coating, which can be as thick as 4 nm, stabilizes the interface between the electrode active material (e.g., NCM) and the solid electrolyte (SE) (e.g., Li6PS5Cl). Electrochemical evaluations exemplified herein confirm significant improvements in long-term cycling performance and active mass utilization compared to uncoated NCMs. Therefore, the coating effectively suppresses degradation of the NCM / SE interface, particularly the formation of oxidative species. Furthermore, polymer coating (e.g., using poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)), PVBTA-TFSI) reduces the degree of particle cracking. Overall, the experimental results illustrate a scalable process for novel polycation coatings onto NCMs for next-generation SSBs.

[0003] Polymer coatings for electrode materials are known in the prior art. However, known polymer coatings are based on neutral polymers (e.g., PVP, polyvinylpyrrolidone), as described in, for example, US2022 / 0069337A1 and WO2021 / 254215A1. The same polymer (PVP) disclosed in US2022 / 0069337A1 and WO2021 / 254215A1 is used herein as an exemplary reference material according to the prior art to highlight the unexpected and surprising improvement in cycling stability of the present invention disclosed below (see FIG. 13).

[0004] While the coatings disclosed in US2022 / 0069337A1 further require photocuring to form the final coating, the coatings of the present invention disclosed herein below do not require photocuring, thereby significantly reducing the complexity of producing the coatings over the prior art.

[0005] WO 2021 / 254215 A1 only mentions the ionic compound as being contained in the binder polymer, and therefore states that the ionic compound is only suitable for optimizing the binder polymer. The binder polymer itself is merely an auxiliary compound for optimizing the mechanical properties of the coating disclosed in WO 2021 / 254215 A1. WO 2021 / 254215 A1 does not suggest that the binder polymer exerts any technical effect beyond improving mechanical properties. In contrast, the polyelectrolyte polymer according to the present invention disclosed herein actually exerts a technical effect in optimizing cycle stability, as will be shown below. The polyelectrolyte polymer according to the present invention disclosed herein is not merely a type or part of an auxiliary binder polymer, but is a material that exerts a technical effect. Therefore, WO 2021 / 254215 A1 does not provide any suggestion regarding the subject matter of the invention disclosed herein below.

[0006] Solid-state lithium batteries (SSBs) use solid electrolytes (SEs) instead of organic liquid electrolytes, and are expected to fundamentally resolve battery safety issues, making them ideal chemical power sources for electric vehicles and large-scale energy storage. To achieve higher energy density, intercalation-type cathode active materials and thiophosphate-based SEs have attracted attention. LiNi, a high-nickel ternary cathode material, has also been used. 1-x-y Co x Mn yO2(NCM) is considered a promising lithium battery cathode material that combines high energy density and low cost. However, when NCM is used with thiophosphate-based SEs, severe capacity loss due to interfacial degradation is observed. Generally, the interfacial degradation reaction between NCM and SEs results in a harmful interfacial layer that hinders the transport of lithium ions and electrons. Even at zero charge, chemical reactions occur at the NCM / SE interface, causing detrimental capacity loss.

[0007] During the charging process of the first cycle, the potential window of the thiophosphate-based SE is narrow, which slows down lithium transport due to electrochemical degradation at the interface with the solid electrolyte. However, during the discharging process, the potential window is narrow, and the lithium transport rate is slowed down due to electrochemical degradation at the interface with the solid electrolyte. + The oxidation of SEs often reaches 0.1 / Li, which is not low enough to cause a reduction reaction. Therefore, the oxidation of SEs is significantly slowed down in subsequent cycles. Because thiophosphate-based SEs are in direct contact with the NCM, oxygen and lithium atoms in the surface region of the NCM undergo side reactions with the electrolyte, leading to structural degradation of the NCM surface and the passivation layer between the NCM and SE. At the NCM / SE interface, SO was detected by time-of-flight secondary ion mass spectrometry (ToF-SIMS). x n- and PO x n- Oxidizing species such as SiO2 can be detected by differential electrochemical mass spectrometry during cycling. Loss of oxygen leads to mechanical cracking and plays an important role in interfacial degradation. While lattice contraction and expansion of NCMs contribute to capacity loss, SSBs are more adversely affected than lithium-ion batteries (LIBs) by loss of contact between SEs and the cathode material. Therefore, research efforts to improve the stability of the electrode-electrolyte interface have been ongoing but have so far been unsuccessful.

[0008] To enhance the interfacial stability between NCMs and thiophosphate-based SEs, surface modification by coating on NCMs has been extensively investigated. Generally, wet coating and dry coating processes are difficult to form thin and uniform coating layers compared to atomic layer deposition (ALD). Therefore, atomic layer deposition methods such as HfO2-coated NCMs have also been investigated. Coating materials include LiNbO3, Li6ZnNb4O, and others. 14 , LiAlO2, Li2ZrO3, Li4Ti5O 12 , and Li3B 11 O 18 Much research has focused on inorganic oxides such as ZnO. Because these inorganic coatings are hard and brittle, they are prone to breakage when subjected to mechanical stress, such as during the cyclic charge-discharge process of a battery. Therefore, it is impossible to provide an inorganic coating that can withstand mechanical stress and completely cover the surface of an electrode active material. Compared to inorganic coatings, polymer coatings are relatively soft, and if forces are exerted between the functional groups and the NCM, they can uniformly cover the substrate. For example, polyvinylpyrrolidone (PVP) can function as a surfactant to modify the surface of metal oxides. While poly(3,4-ethylenedioxythiophene) modification of NCMs and carbon additives in SSBs via molecular layer deposition have been investigated, polymer-coated NCMs have primarily been utilized in lithium-ion batteries using liquid electrolytes. The possibility of combining polymer coatings of NCMs with solid electrolytes, particularly thiophosphate-based solid electrolytes, was previously unknown and unexpected. A previously unaddressed and unresolved issue in the polymer coating of NCMs with polyelectrolyte polymers is the need for solvent stability for the NCM. That is, the solvent used to dissolve the polyelectrolyte polymer in the coating process is + This means that it must not dissolve (extract) ions.

[0009] The polyelectrolyte polymers, or polyelectrolyte organic polymers, of the present invention include polycationic and polyanionic polymers (also synonymously referred to as polycationic organic polymers or polyanionic organic polymers, or cationic polymers, cationic organic polymers, anionic polymers, and anionic organic polymers). All types of polyelectrolyte polymers include polymers composed of monomers bearing one or more charged functional groups (and counterions). The charged functional groups may or may not participate in the polymerization reaction. That is, the polymer molecules of polyelectrolyte polymers achieve a polyelectrolyte structure (polycationic or polyanionic) by polymerizing monomers bearing at least one charged functional group per monomer moiety. As known in the art, to be a polyelectrolyte polymer (polycationic or polyanionic), the monomers do not need to already contain multiple charged functional groups. The polyelectrolyte structure is achieved by polymerization of the monomers, regardless of the number or type of charged functional groups they contain.

[0010] Furthermore, it is not essential that all of the monomers constituting the polyelectrolyte polymer according to the present invention have at least one charged functional group (and counter ion). The polyelectrolyte polymer according to the present invention can also be a copolymer composed of one or more monomers having at least one charged functional group and one or more polymers having no charged functional group, and the polyelectrolyte polymer is formed by copolymerization of at least one monomer having at least one charged functional group and at least one monomer having no charged functional group.

[0011] In accordance with prior art usage, polyelectrolyte polymers (polycationic polymers, polyanionic polymers) are also referred to herein synonymously as cationic organic polymers or anionic organic polymers. This is because, even if the monomer or one of the monomers (in the case of a copolymer) has only one charged functional group, it is impossible for the polymer to have only one charged functional group per polymer molecule upon polymerization. Therefore, polycationic polymers / cationic polymers and polyanionic polymers / anionic polymers are well-known synonymous combinations.

[0012] When handling NCMs, contact with water must be avoided. However, cationic (or polycationic) polymers such as PVBTA-Cl and LiTFSI are soluble only in water or other polar organic solvents, and NCMs are not stable in these solvents. On the other hand, when PVBTA-Cl is ion-exchanged to form PVBTA-LiTFSI, PVBTA-TFSI surprisingly dissolves in acetone rather than water. NCMs are stable in acetone solutions of PVBTA-TFSI and are easy to handle by spray-drying. This novel and unprecedented approach successfully coated NCMs with polymers without affecting their stability. It will be apparent to those skilled in the art that these results obtained in the example of the combination of PVBTA-TFSI and NCM can also be applied to other polycationic polymers combined with other cathode active materials (e.g., NCA) without departing from the scope of the present invention.

[0013] Furthermore, as will be apparent to those skilled in the art, the present invention is applicable not only to solid electrolytes, but also to liquid and polymer electrolytes. In either case, mechanical degradation of the NCM leads to particle cracking during cycling, and the coating of the present invention helps suppress this degradation mechanism. Thus, the present invention can be advantageously applied to all batteries using any type of electrolyte without departing from its scope. DETAILED DESCRIPTION OF THE INVENTION

[0014] [Contents of the invention] An object of the present invention is to provide a polymer-coated electrode active material that can be easily and inexpensively prepared and that exhibits very high cycling stability in electronic devices such as batteries.

[0015] This high cycling stability is due, for example, to the presence of phosphate (PO), a species known as a decomposition product of thiophosphate-based solid electrolytes in solid-state lithium-ion electrochemical cells. x - ) and / or sulfate / sulfite (SO x - Higher cycling stability is also evidenced by the finding that untreated NCM cells exhibit more intra- and inter-(sintered) NCM particle crazes and cracks compared to cells prepared with coated NCM particles.

[0016] Electrode active materials, as understood herein, include cathode active materials and anode active materials. Cathode active materials are preferred electrode active materials, and among the cathode active materials, high nickel ternary cathode materials, LiNi 1-x-y Co x Mn y O2(NCM) is the most preferred electrode active material.

[0017] The thiophosphate-based solid electrolyte according to the present invention is an argyrodite-type thiophosphate, such as Li6PS5Cl (LPSCl), and Li 7+o-p M IV o M V 1-o Ch 6-p X p Type thiophosphate (M IV = Si, Ge, Sn; M V = P, Sb; Ch = O, S, Se; X = Cl, Br, I, BH4, and 0≦o≦1; 0≦p≦2). Besides the thiophosphate-based solid electrolytes, other solid electrolytes, such as Li 1+xAl x Ti 2-x NaSICON type such as (PO4)3(LATP), Li7La3Zr2O 12 Garnet-type (LLZO) and Li 3x La 2 / 3-x Perovskite type such as TiO3(LLTO), Li 10 GeP2S 12 A solid electrolyte such as LGPS type can be used.

[0018] Surprisingly, the polymer coating of the electrode active material according to the invention allows for the reduction of SO 2 in, for example, thiophosphate-based solid electrolytes or, for example, on the surface of NCMs. x n- and P.O. x n- It was found that the formation of oxidative species such as , is efficiently reduced, which significantly and effectively improves the cycling stability of the electrode active material.

[0019] Therefore, to achieve the above object, the present invention provides a polymer coating for an electrode active material, an electrode active material provided with the polymer coating, and the use of the material in an electronic device, such as a battery, in particular a solid-state lithium-ion battery or solid-state lithium-ion electrochemical cell.

[0020] The polymeric coating according to the present invention may comprise a thermoplastic polymer, or a non-thermoplastic polymer, or a combination of both types of polymer.

[0021] Besides the use of polycationic organic polymers for coating NCMs, the scope of the present invention also includes polyanionic organic polymers such as poly(acrylic acid), graphene oxide, polysaccharide gums such as xanthan gum, poly(vinyl alcohol), polydopamine, chitosan, sulfonated tetrafluoroethylene-based fluoropolymer-copolymers, poly(styrene sulfonate), poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, sulfonated polyphenylene sulfone, copolymers with sulfonated polyphenylene sulfone, sulfonated poly(2,6-dimethyl-1,4- Also included are sulfonated polymers such as poly(phenylene oxide), poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide], poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide], sulfonated poly(ether ether ketone), poly(3-sulfopropyl methacrylate), and poly[(4-styrenesulfonyl)(fluorosulfonyl)imide]; and phosphonated polymers such as poly(vinylphosphonic acid), polyphosphonates, and poly([2-(methacryloyloxy)ethyl]phosphate). This list of polyanionic organic polymers is not intended to limit the scope of the invention. Suitable counterions for polyanionic organic polymers include aluminum(III), barium(II), beryllium(II), calcium(II), chromium(III), copper(I), copper(II), gold(I), gold(III), hydrogen(I), iron(II), iron(III), lead(II), lead(IV), lithium(I), magnesium(II), manganese(II), manganese(III), manganese(IV), mercury(II), potassium(I), silver(I), sodium(I), strontium(II), tin(II), tin(IV), zinc(II), polyatomic cations such as ammonium, hydronium, mercury(I), Li + Na + K + Ca 2+ Mg 2+ Al 3+ Polyatomic cation, NH4 + , ammonium derivative, NR3H +, NR2H2 + , NRH3 + R is independently selected from the list including alkyl, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, and isopentyl. This list is also not intended to limit the scope of the invention.

[0022] It has been found that similarly favorable long-term stability of NCMs can be achieved by combining each type of polyelectrolyte polymer with one or more neutral polymers to form a diluted polyelectrolyte polymer (i.e., a polyelectrolyte polymer combined with a neutral polymer). As used herein, combining each type of polyelectrolyte polymer with at least one neutral polymer refers to mechanically mixing the different polymers, e.g., via blending, co-solution, etc., or chemically combining the polymers, e.g., via copolymerization, etc. Thus, copolymers of polycationic and neutral organic polymers, or copolymers of polyanionic and neutral organic polymers, are also polycationic or polyanionic organic polymers according to the present invention. Suitable neutral polymers are those containing at least one amide group per molecular moiety of the neutral polymer, with the at least one amide group being located within the main chain or a side chain of the polymer chain of the neutral polymer. Examples of suitable neutral polymers include polyvinylpyrrolidone, poly(N-vinylformamide), and polyamides. This exemplary list should not be understood as limiting the scope of the invention.

[0023] The polymer coatings disclosed herein are particularly useful for coating NCMs used with thiophosphate-based solid electrolytes in solid-state lithium-ion batteries / electrochemical cells. In another embodiment, the polymer coatings disclosed herein are also useful for coating NCMs used with liquid or polymer electrolytes, for example, in lithium-ion batteries. Unlike inorganic coatings, when combined with a liquid electrolyte, polymer coatings swell with the liquid electrolyte, reducing the resistance and increasing the capacity of the battery. Some polymers with specific functional groups, such as poly(ethylene carbonate), can even increase the lithium transport number. Similarly, polymer electrolytes are more compatible with polymer coatings than inorganic coatings.

[0024] Polyelectrolyte polymers according to the present invention can also be prepared by oxidizing, reducing, protonating, and / or ion-exchanging an uncharged base polymer to form a polycationic or polyanionic polymer through these reactions.

[0025] To achieve a uniform coating, the invention disclosed herein teaches the use of spray-dried polyelectrolyte solutions, particularly for coating electrode active materials such as NCM materials. Spray drying can be classified as a wet-coating method applied in industry. Furthermore, because polyelectrolytes can easily adsorb onto metal oxides through electrostatic interactions, poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide)) (PVBTA-TFSI) is utilized as an example of a coating material for NCMs according to the invention described herein, and this example is not intended to limit the scope of the invention. PVBTA-TFSI is uniformly coated on the surface of NCMs, and the cycling performance of PVBTA-TFSI-coated NCM battery cells is significantly improved compared to untreated NCM cells. Without being bound by any particular theory, the present specification provides a detailed explanation of important physical phenomena, such as contact loss, electrochemically inactive interfacial layers, and lithium diffusion pathways, by discussing exemplary applied cathode composites and their electrochemical performance results.

[0026] Overall, comparison of oxidative degradation products by ToF-SIMS confirmed that polymer coating, using, for example, PVBTA-TFSI, significantly improved the interfacial stability of the CAM / SSE interface, consistent with the electrochemical data presented herein. PVBTA-TFSI was synthesized as an exemplary polymer according to the present invention by free radical polymerization and used to coat NCMs by spray drying, a scalable and controllable process. TEM and Tof-SIMS showed that 1 wt % of the polymer formed a homogeneous coating approximately 4 nm thick. In terms of electrochemical analysis, the exemplary PVBTA-TFSI coating on the NCM surface improved the cycling stability of thiophosphate-based SSBs. Correspondingly, EIS and active mass calculations revealed that the polymer coating reduced interfacial degradation. Furthermore, Tof-SIMS demonstrated a lower amount of oxidative species formed at the interface of the polymer-coated NCM, supporting the electrochemical data. Meanwhile, FIB-SEM confirmed the GITT and lithium diffusion length calculations, demonstrating that the polymer coating reduced particle cracking within the NCM. Overall, polymer coatings such as PVBTA-TFSI improve cycling stability by reducing mechanical degradation and act as a protective layer to reduce interfacial degradation.

[0027] NCM coated with lithium-based anionic polyelectrolyte is also a crucial solution to address the capacity loss at the NCM / SE interface, which improves the overall performance of NCM in SSB. Polyvinylpyrrolidone (PVP) can form a strong interfacial bond between the cathode material and the lithium-based anionic polyelectrolyte through electrostatic forces. Therefore, we combined the above ideas and introduced the first polymer composite coated NCM for SSB in this study. A blend of PVP and lithiated polyphenylene sulfone sulfonate (LiPPSS) was coated on LiNi 0.9 Mn 0.05 Co 0.05We have used LiPPSS / PVP-NCM90 as a coating material for O2 (NCM90). Spray drying, which exploits the electrostatic interactions between LiPPSS, PVP, and NCM90, was used to achieve a uniform, thin polymer coating on NCM90. The use of this thin LiPPSS / PVP polyelectrolyte complex or diluted polyelectrolyte polymer coating on NCM90 not only minimizes contact loss but also optimizes cycling performance. Furthermore, we have investigated the interfacial degradation and the lithium diffusion path length within the cathode composite, providing further evidence of improved electrochemical performance.

[0028] <Characteristics of anionic polymer coated NCM90> In our study on the use of polyanionic polymers, we employed a methodology similar to that applied in our polycationic polymer experiments, using a spray coating method to apply anionic polymer coatings to NCM90. Previous studies have concluded that 1 wt% polymer (relative to the weight of NCM90) provides the optimal coating thickness, leading to excellent electrochemical performance and the most uniform coating layer. Therefore, we used the spray coating method described below, using 1 wt% polymer (relative to the weight of NCM90) as a standard for comparison. However, the water and alcohol solvents in the coating process contribute to the removal of Li from the NCM. +It has been observed that the use of these solvents can cause the dissolution of NCM90, and the use of these solvents should be avoided. To address this issue, we first used lithiated polyphenylene sulfone sulfonate (LiPPSS) to coat NCM90, thereby making it easily soluble in dimethylformamide (DMF). Furthermore, sulfonated poly(phenylene sulfone), which has a highly electron-deficient aromatic ring, exhibits superior thermal and thermo-oxidative stability compared to other sulfonated poly(arylenes). However, energy-selective backscattering (ESB) detection coupled to a scanning electron microscope (SEM) revealed non-uniform coating, characterized by the detachment of certain polymer particles from the NCM90 surface, as shown in Figure 19. This result suggests that the electrostatic forces between LiPPSS and NCM90 are insufficient to achieve uniform coating.

[0029] Further investigation using infrared spectroscopy reveals that PVP exhibits a strong electrostatic attraction with LiPPSS, as shown in Figure 20, where the C=O stretch occurs at 1669 cm -1 From 1656cm -1 This is confirmed by a blue shift to the LiPPSS-PVC complex. Unlike polyanions such as polyacrylic acid (PAA), which tend to precipitate immediately upon mixing with PVP, when PVP and LiPPSS are dissolved, these two polymers form a stable, transparent solution, and the composite polymer particles do not separate. This characteristic is advantageous in the spray-drying process. A 1:1 weight ratio between PVP and LiPPSS was then established for coating NCM90. This material is hereafter referred to as LiPPSS / PVP-NCM90. As shown in Figure 19, ESB and SEM images of LiPPSS / PVP-NCM90 demonstrate a significant reduction in the surface polymer particles. This observation indicates uniform and homogeneous coating of NCM90 using the LiPPSS / PVP composite material.

[0030] <Evaluation of rate characteristics> As shown in Figure 21, the rate performance of coated NCM90, including 1 wt% polyvinylpyrrolidone-coated NCM90 (PVP-NCM90), LiPPSS / PVP-NCM90, 1 wt% poly((4-vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonylimide))-coated NCM90 (PVBTATFSI-NCM90), and 1 wt% polymethyl methacrylate-coated NCM90 (PMMA-NCM90), was compared with that of untreated NCM90 (pNCM90) under different conditions: 0.1 C, 0.25 C, 0.5 C, and 1 C, and then back to 0.1 C. The evaluation utilized a pellet-type SSB, NCM / Li6PS5Cl / VGCF||Li6PS5Cl||In-Li. VGCF is a registered trademark.

[0031] In Figure 21, the PVP-NCM90 SSB exhibited only a discharge capacity of 138 mAh / g and a coulombic efficiency of 70% in the first 0.1 C cycle, which was significantly lower than those of the pNCM90 SSB (183 mAh / g and a coulombic efficiency of 77%), the PVBTATFSI-NCM90 SSB (170 mAh / g and a coulombic efficiency of 79%), and the LiPPSS / PVP-NCM90 SSB (188 mAh / g and a coulombic efficiency of 80%). Furthermore, the PVP-NCM90 SSB exhibited poorer rate performance than the LiPPSS / PVP-NCM90 and pNCM90 SSB at all C rates. Without being bound by any particular theory, this may be due to the PVP coating layer, which has no charge or ion conductivity, possibly impeding lithium ion transport. However, the relatively low capacity of the PVP-NCM90 SSB suggests that the entire NCM90 surface was not completely covered. This difference may be due to the cell fabrication process, such as cathode composite mixing and cell pressing, which may cause the PVP coating to peel off or be damaged, resulting in the exposure of the surface of NCM90. A similar effect can be observed with PMMA-NCM90, which has a much lower capacity (156 mAh / g and coulombic efficiency of 74%) than pNCM90, PVBTATFSI-NCM90, and LiPPSS / PVP-NCM90 in the first cycle.

[0032] In the first cycle shown in Figure 21, the LiPPSS / PVP-NCM90 SSB showed a lower charge capacity (234 mAh / g) at a 0.1 C rate compared to the pNCM90 SSB (237 mAh / g). However, the discharge capacity (188 mAh / g) and coulombic efficiency (80%) at a 0.1 C rate exceeded those of the pNCM90 SSB (183 mAh / g and 77% coulombic efficiency) in the first cycle discharge process. The improved discharge capacity and coulombic efficiency of the LiPPSS / PVP-NCM90 SSB may be due to the reduction of side reactions that the LiPPSS / PVP composite coating may promote.

[0033] FIG. 22 shows that the LiPPSS / PVP composite coating reduces the electrochemical side reactions of Li6PS5Cl in the initial charging process below 3 V. Furthermore, for both the LiPPSS / PVP-NCM90 SSB and the pNCM90 SSB, the side reactions exceed 3.48 V (vs. Li + / Li-In), or about 4.1V (vs. Li + The areas under the dQ / dE plots of (Li / Li) were comparable during the first cycle charging step, indicating that the coating did not interfere with the H2 + H3 phase transition process. Furthermore, when the LiPPSS / PVP-NCM90 SSB was evaluated at different discharge rates, specifically 0.25 C, 0.5 C, and 1 C, its rate performance showed significant improvement compared to pNCM90 and other coated NCM90 SSBs. This improvement may be due to the LiPPSS / PVP composite coating layer being more pronounced and effective at higher C rates. Furthermore, at the 25th cycle, the LiPPSS / PVP-NCM90 SSB exhibited superior reversibility compared to pNCM90 SSB, as shown in Figure 23. In conclusion, the LiPPSS / PVP-NCM90 SSB consistently outperformed pNCM90 and other coated NCM90 SSBs at all C rates. The superior performance of LiPPSS / PVP-NCM90 SSB may be due to the reduction of side reactions without sacrificing the H2+H3 phase transition process by the introduction of LiPPSS / PVP composite coating.

[0034] <Calculation of cycle performance and active mass> To investigate the 0.1 C cycling performance more closely, we constructed LiPPSS / PVP-NCM90 and pNCM90 SSBs consisting of NCM / Li6PS5Cl / VGCF||Li6PS5Cl||In-Li, allowing for direct comparison.

[0035] Figure 24 compares the 0.1C cycling performance between LiPPSS / PVP-NCM90 and pNCM90 cells. Initially, LiPPSS / PVP-NCM90 exhibits a discharge capacity of 190 mAh / g, while pNCM90 exhibits a lower value of 180 mAh / g. After 100 0.1C cycles, LiPPSS / PVP-NCM90 retains the highest capacity at 78.3%, while pNCM90 only retains approximately 69%. After the 152nd cycle, the capacity retention of LiPPSS / PVP-NCM90 is 71.6%, while that of pNCM90 remains at approximately 59.6%. The superior capacity retention of LiPPSS / PVP-NCM90 indicates that the 1 wt% LiPPSS / PVP composite coating layer improves the long-term cycling stability of NCM in SSBs.

[0036] Figure 25 shows a comprehensive comparison of the active mass calculation results (shown in Figure 26) based on the references. In this study, active mass refers to the amount of active material involved in the reaction.

[0037] LiPPSS / PVP-NCM90 showed an active mass retention of 83.7% after 152 cycles, while pNCM showed a lower retention of 78.8%. The decrease in active mass was mainly due to significant contact loss. Therefore, the LiPPSS / PVP composite coating of NCM in SSB can significantly improve overall performance by suppressing detrimental contact loss. The term "contact loss" is used to encompass two fundamental surface degradation mechanisms that affect battery performance. These are the formation of an electrochemically inactive interfacial layer due to undesirable side reactions (including chemical, electrochemical, and chemomechanical degradation), and physical separation between the NCM electrode and the Li6PS5Cl electrode. These mechanisms reduce the effective contact area between the NCM and Li6PS5Cl during cycling, resulting in active mass loss and increased interfacial resistance. Although distinct, both contact loss mechanisms have similar effects on battery performance, making them difficult to distinguish experimentally.

[0038] In contrast, factors such as a passivation layer that hinders the transport of lithium and electrons, or cracks in the particles within NCM, can extend the lithium diffusion path and may hinder efficient Li + transport during battery cycling. This increase in the length of the lithium diffusion path creates a difference in the values of cycle performance and active mass retention rate. An appropriately optimized coating can effectively suppress interfacial degradation and particle cracking. This forms a stable interface and ensures a shorter and unobstructed lithium diffusion path. Examples in the detailed embodiments of the present invention explain the mechanism by which the LiPPSS / PVP composite coating promotes a stable interface and maintains a shorter and unobstructed lithium ion diffusion path, thereby improving battery performance.

[0039] <Stable window between PEDOT and Li6PS5Cl> To evaluate the electrochemical compatibility of poly(3,4-ethylenedioxythiophene) (PEDOT) and polyethylene glycol (PEO) with Li6PS5Cl, VGCF is coated with PEDOT or PEO using the aforementioned spray drying method. Then, this coated VGCF is used as the working electrode to identify potential side reactions. The electrochemical stability is tested by cyclic voltammetry in the range of 0 V to 4 V (vs. Li + / Li-In) with VGCF / Li6PS5Cl as the working electrode, a Li-In alloy as the reference electrode and the counter electrode. Comparing the current density and onset potential among uncoated, PEDOT-coated, or PEO-coated VGCFs, significant peak currents were detected at approximately 3.7 V (vs. Li + / Li-In) for both PEDOT and PEO. This suggests that neither PEDOT nor PEO is electrochemically stable with respect to Li6PS5Cl and is unsuitable for coating applications (see Figure 27).

[0040] [Detailed Embodiments of the Invention] A person skilled in the art well understands that when a range of values (e.g., time, temperature, particle size, concentration, BET specific surface area, etc.) is indicated, it does not mean only the explicitly indicated range, but also all other sub-ranges within the explicitly indicated range are intended and are implicitly indicated in the present disclosure.

[0041] <Exemplary Reagents and Materials> Vinylbenzyltrimethylammonium chloride (VBTA-Cl) monomer, reagent-grade sodium persulfate (Na2S2O8) initiator, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and vapor-grown carbon fiber (VGCF) are purchased from Sigma-Aldrich. Single-crystal high-nickel NCM83 (LiNi 0.83 Mn 0.06 Co 0.11 O2) is purchased from MSE Supplies (particle size of about 3 - 5 μm, BET specific surface area of about 0.5 - 0.9 m 2 / g). Li6PS5Cl (LPSCl) is purchased from NEI. Indium foil is purchased from chemPUR with a thickness of 100 μm and punched into circular electrodes with a diameter of 9 mm. Lithium foil is purchased from Albemarle Rockwood Lithium with a thickness of 125 μm and punched into circular electrodes with a diameter of 6 mm.

[0042] <Exemplary Synthesis of PVBTA-TFSI> Poly(vinylbenzyl)trimethylammonium bis(trifluoromethanesulfonyl)imide (PVBTA-TFSI) was synthesized via the route shown in Figure 1. First, 5 g of vinylbenzyltrimethylammonium chloride (VBTA-Cl) and 0.3 ml of saturated NaSO solution were mixed in 20 ml of deionized water, followed by heating at 75 °C for 48 hours under N purging (molar ratio of VBTA-Cl:NaSO:1:0.3). After polymerization, PVBTA-Cl was purified by dialysis against a large amount of deionized water and further concentrated using a rotary evaporator. The concentrated polymer solution was then added dropwise to a LiTFSI solution (7.5 g of LiTFSI dissolved in 20 g of deionized water) and stirred overnight for ion exchange. PVBTA-TFSI immediately precipitated when PVBTA-Cl was added dropwise to the LiTFSI solution. After the ion exchange reaction, the PVBTA-TFSI was washed three times with deionized water using a centrifuge to remove residual LiTFSI and separate the PVBTA-TFSI solids. The PVBTA-TFSI was then dried in a vacuum oven at 80 °C for 72 hours and then stored in a glove box. 1 H NMR (400 MHz, deuterated acetone): δ 1.36–1.99 (H1, H2), δ 2.05 (acetone-d6), δ 3.14 (H6), δ 4.4–4.9 (H5), δ 6.5–7.4 (H3, H4). FT-IR (cm) of PVBTA-TFSI -1 ):973(CN expansion / contraction), 1346,1326,1176,1132,1050(TFSI - ), 1612, 1480, 1422 (aromatic C=C stretching), 3043, 2922, 2852 (alkyl CH stretching), 3400 (H2O). FT-IR (cm) of PVBTA-Cl -1 ): 973 (CN stretching), 1612, 1480, 1422 (aromatic C=C stretching), 3015, 2922, 2852 (alkyl CH stretching), 3400 (H2O). FT-IR of LiTFSI (cm -1 ):1327 (SO2 asymmetric stretching), 1245 (CF3 symmetric stretching), 1204 (CF3 asymmetric stretching), 1147 (SO2 symmetric stretching), 1065 (asymmetric S2N stretching).

[0043] <Exemplary Preparation of PVBTA-TFSI Coated NCM> Using BUCHI's Mini Spray Dryer B-290, as shown in Fig. 1, PVBTA-TFSI is coated on NCM. As a precursor, 0.1 g (5 wt% with respect to NCM) or 0.02 g (1 wt% with respect to NCM) of the polymer is mixed with 2 g of NCM and 30 g of acetone. The mixing process is carried out by vigorous stirring and takes about 1 hour to surely decompose particle aggregation into smaller sizes. The inlet temperature is 150 °C, the volumetric flow (i.e., suction of the vacuum pump) is 37 m 3 / h, the supply rate of the polymer solution is 8 mL / min, and the N2 flow is 40 L / min. The spray drying conditions are optimized so that the highest productivity can be obtained at about 50 - 70 wt%. Also, 5 wt% polymer coated NCM and 1 wt% polymer coated NCM are denoted as 5P-NCM and 1P-NCM, respectively. Furthermore, 5 wt% PVP coated NCM follows the same process as above except that ethanol is used as the solvent.

[0044] <X-ray Diffraction (XRD)> Using Panalytical Empyrean XRD with CuKα radiation, PVBTA-TFSI is characterized, and XRD is used to confirm the chemical stability between PVBTA-TFSI or LiTFSI and LPSCl. The diffraction pattern is collected in the range of 2θ angles from 10° to 85° with a step size of 0.026°, a solar slit of 0.04 radians, and a 1 / 2° anti-scattering slit. To confirm the chemical stability between PVBTA-TFSI or LiTFSI and LPSCl, PVBTA-TFSI or LiTFSI is mixed with LPSCl at a weight ratio of 1:1 (total about 500 mg) by grinding using an agate mortar, and then pressed into a pellet (8 mm in diameter). Then, the pellet is heated and maintained at 80 °C for 24 hours, and then the pellet is powdered by the grinding process in the agate mortar. Finally, the powdered sample after heating is characterized by XRD.

[0045] <Thermogravimetric Analysis (TGA)> The TGA measurement was carried out on a sample of about 20 mg using a STA 409 PC (Netzsch-Geraetebau) in the temperature range of 25 °C to 1000 °C under air / O2 at a heating rate of 10 °C / second.

[0046] < 1 1H nuclear magnetic resonance ( 1 1H NMR) The 1H NMR spectrum of PVBTA-TFSI was recorded at 400 MHz in deuterated acetone using a Bruker Avance II. 1 The 1H NMR spectrum of PVBTA-TFSI was recorded at 400 MHz in deuterated acetone using a Bruker Avance II.

[0047] <Fourier transform infrared spectroscopy (FT-IR)> The FT-IR spectra of PVBTA-TFSI, PVBTA-Cl, and LiTFSI were recorded with a total of 96 scans using an ATR-FTIR Thermo Fischer Scientific iD5 ATR spectrometer (550 - 4000 cm -1 -1). To confirm the chemical stability between PVBTA-TFSI or LiTFSI and LPSCl, PVBTA-TFSI or LiTFSI was mixed with LPSCl in an agate mortar and then pressed into a pellet. Then, the pellet was heated and maintained at 80 °C for 24 hours. Before and after the heating process, the FT-IR spectrum was measured in the form of the pellet.

[0048] <Brunauer-Emmett-Teller analysis (BET)> The specific surface area of the polymer-coated and untreated NCM was calculated by the BET method. Before measurement, the sample was evacuated at 120 °C for 12 hours in a standard glass tube. Then, BET measurements were performed using an automatic gas adsorption station (Autosorb-1-MP, Quantachrome Instruments) maintained at 77 K with liquid nitrogen in a standard cryostat.

[0049] <Scanning electron microscopy (SEM)> The morphology of the NCMs was characterized using a SEM (Merlin, Zeiss) at an accelerating voltage of 3 kV and an accelerating current of 200 pA. Backscattered electron images and secondary electron SEM images were taken using the SEM. For sample preparation, the polymer-coated and untreated NCMs were measured in powder form, firmly adhered to conductive carbon tape.

[0050] <Focused ion beam scanning electron microscopy (FIB-SEM)> Cross sections of the coated and untreated NCM powders, as well as the cathode composite pellets, were analyzed using an XEIA Xe-Plasma FIB (TESCAN). Sample preparation involved milling the FIB craters without polishing using a 1 nA Xe ion beam at low angles while maintaining the samples in liquid nitrogen at -135 °C. Backscattered electron images and secondary electron SEM images were then taken at an accelerating voltage of 3 kV and an accelerating current of 200 pA.

[0051] Energy Dispersive X-ray Spectroscopy (EDS) After SEM or FIB-SEM measurements, the coating layer on the NCM was characterized using energy dispersive X-ray spectroscopy (X-Max-Extreme detector, Oxford Instruments). However, to obtain a more accurate signal from EDS, the accelerating voltage and current were increased to 5 kV and 2 nA, respectively. The working distance was controlled to 5.5–5.6 mm. The target elements were carbon and sulfur.

[0052] <Transmission Electron Microscopy (TEM)> The TEM images were bright-field images to maximize the contrast between the inorganic core and the organic coating of the electrode active material. The methods for producing such images are well known in the art and will not be described further here. The TEM instrument used was a TVIPS TEMCam XF416FS camera mounted on a JEOL JEM-3010 microscope, operating at an accelerating voltage of 300 kV.

[0053] <Time-of-flight secondary ion mass spectrometry (ToF-SIMS)> ToF-SIMS technology is well known in the art and will not be described further here. The instrument used was an M6 Hybrid SIMS (IONTOF) equipped with a 30 kV Bi cluster primary ion gun for analysis and a 5 kV Ar gas cluster source (GCIB) for depth profiling (sputtering). Samples were prepared in a glove box and transferred to the measurement chamber using a LEICA EM VCT500 shuttle (Leica Microsystems). The software package SurfaceLab 7.2 (IONTOF) was used to evaluate the ToF-SIMS data.

[0054] <Electrode composite material and cell assembly> All cell tests were conducted using a pellet-type cell casing. First, 60 mg of LPSCl was pressed into a pellet within a PEEK cylindrical insulator. Next, 70 wt% untreated or coated NCM, 30 wt% LPSCl, and 1 wt% additional VGCF were mixed in an agate mortar for approximately 20 minutes to create the cathode composite. Next, 12 mg of the cathode composite was pressed onto one side of the electrolyte. Finally, indium foil (100 μm thick, 9 mm diameter) and lithium foil (125 μm thick, 6 mm diameter) were pressed onto the other side as the anode. After assembling the entire cell stack, it was pressed at 30 kN for 3 minutes to obtain a solid electrolyte of approximately 400 μm thick with approximately 30 μm of cathode composite. Before electrochemical analysis, the entire cell was analyzed on an external aluminum framework (~50 MPa).

[0055] Further illustrative details: For cyclic voltammetry, an asymmetric cell with the following composition was prepared: InLi | Li6PS5Cl | Li6PS5Cl, carbon fiber. To prepare 100 mg of the cathode composite, 9.09 mg (9.1% by weight) of VGCF was added to 90.90 mg of Li6PS5Cl and mixed in a mortar for 15 minutes. To prepare the cell for analysis, 80 mg of Li6PS5Cl was pressed into a pellet as a separator within a PEEK cylindrical insulator. 30 mg of the Li6PS5Cl-carbon fiber composite was pressed onto one side of the electrolyte. Finally, indium foil (100 μm thick, 9 mm diameter) and lithium foil (125 μm thick, 6 mm diameter) were pressed onto the other side as the anode. After cell assembly, the entire cell stack was pressed at 30 kN for 3 minutes. The entire cell was placed within an external aluminum framework (approximately 50 MPa) before electrochemical analysis.

[0056] <Electrochemical analysis> The battery voltage is 2.0 to 3.7 V (vs. Li) at 25°C. + The battery is charged and discharged within a voltage range of 3.15 V (vs. Li / Li-In) to measure cycle stability, chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). Cycle stability is measured using a MACCOR electrochemical workstation. EIS and CA are also measured using a VMP-300 (BioLogic) electrochemical workstation. The entire procedure is also shown in Figure 2. Two different currents, 0.1 C and 0.25 C, are used in the cycle test, but EIS measurements are performed at 0.1 C. First, the battery is charged to 3.15 V (vs. Li / Li-In). + / Li-In), and then charge to 3.15V (vs. Li) until the current drops to less than 1%. + / Li-In) to maintain CA. Then, 3.15V (vs. Li) at 1MHz to 100μHz. +Immediately after CA in (Li-In), EIS is measured. The sine wave amplitude of EIS is applied at 10 mV from 1 MHz to 10 mHz, 5 mV from 10 mHz to 1 mHz, and 3 mV from 1 mHz to 100 μHz. The 0.25C cycle stability is run for 200 cycles, and impedance is measured at the 1st, 2nd, 53rd, 104th, 155th, and 206th cycles at 3.15 V and 0.1C, as illustrated in Figure 3. The 0.1C cycle stability is run for 100 cycles, and impedance is measured at the 1st to 5th, 10th, 30th, 50th, and 100th cycles at 3.15 V and 0.1C, as shown in Figure 4(a). The procedure for fitting the impedance is well-known to those skilled in the art. The low-frequency part is fitted by the finite-space Warburg behavior (Z fs ) having the functions described in the section below. The galvanostatic intermittent titration method (GITT) is measured with a VMP-300 (BioLogic) electrochemical workstation in combination with EIS to determine the diffusion coefficient after 100 cycles at 0.1C. The coated NCM cell and the untreated NCM cell are charged or discharged every 20 minutes, with a 2-hour relaxation provided after each charge or discharge pulse, and the open circuit voltage (V OC ) is recorded. EIS is applied at a sine wave amplitude of 10 mV in the frequency range of 1 MHz to 1 mHz after each relaxation. [[ID=​​​​​​​​​​​​ Polyelectrolytes, such as PVBTA-TFSI, have an affinity for inorganic surfaces and exhibit an electrostatic effect on metal oxide surfaces, suggesting their potential as promising coating materials for inorganic substrates. Consequently, PVBTA-TFSI is used as an exemplary coating material within the present subject matter due to its surprising chemical stability and therefore compatibility with thiophosphate-based solid electrolytes, such as LPSCL. However, because conventional wet-coating methods often result in inhomogeneous coatings on particle surfaces, we introduce a spray-coating method here, which potentially provides a uniform coating for NCM. Figure 1 is a schematic diagram illustrating the polymer synthesis and spray-coating process using NCM / PVBTA-TFSI / acetone as precursors. The precursor is heated to a temperature (e.g., 150 °C) much higher than the boiling point of the solvent (e.g., acetone) and sprayed through a nozzle. The coating process then takes place during the drying process in a drying chamber. Finally, the dried powder is collected in a collection chamber by a vacuum pump. The spray-drying method typically yields two different coating products, depending on the particle size. First, if the particles are smaller than the sprayed droplets, they are encapsulated within the droplets, resulting in a uniform coating. Second, if the particles are larger than the droplets, a large portion of the particle surface remains exposed after drying. Using the BUCHI Mini Spray Dryer B-290, the solution droplets are approximately 25 μm in size, much larger than the NCM particles (approximately 3 μm to 5 μm). Therefore, a uniform coating is achieved according to the present invention, which is preferable in most cases. However, non-uniform coatings resulting in local deviations from the average thickness are also within the scope of the present invention.

[0059] The structure of PVBTA-TFSI is 1 This was confirmed by H NMR spectroscopy and 1 The H NMR spectrum is in perfect agreement with that of PVBTA-TFSI, as shown in Figure 5. After the polymerization and ion-exchange process, the double bond chemical shift ( 1 In the H NMR spectrum, 1The H NMR spectra (δ = 6.71 ppm, 5.82 ppm, 5.26 ppm) completely disappeared, and instead, a new proton absorption peak appeared at δ = 1.5 ppm, indicating the completion of polymerization. Furthermore, in the spectrum of PVBTA-TFSI, aromatic protons (H3, 4), benzyl protons (H5), and trimethylammonium cation protons (H6) were still present, indicating that the polymer backbone structure was stable after anion exchange. Figure 6 shows the IR spectra of PVBTA-Cl and PVBTA-TFSI after anion exchange. Compared to PVBTA-Cl, PVBTA-TFSI exhibited a peak at 1346 cm -1 , 1176cm -1 , 1132cm -1 , and 1050 cm -1 The spectra show new characteristic bands corresponding to the asymmetric SO2 stretch, the asymmetric CF3 stretch, the symmetric SO2 stretch, and the asymmetric SnS stretch, respectively. These new peaks in the PVBTA-TFSI spectrum are attributed to the TFSI anion group, indicating successful anion exchange. XRD was used to determine the presence of a crystalline phase from LiTFSI, as shown in Figure 7. PVBTA-TFSI exhibits only a broad amorphous peak at approximately 20°C. This indicates that PVBTA-TFSI is an amorphous polymer without LiTFSI separation. The chemical stability between NCM and LPSCl was investigated by heating LPSCl and PVBTATFSI at 80 °C for 24 h. The samples before and after heating were then analyzed by XRD and FT-IR measurements, as shown in Figure 8A (FTIR) and Figure 8B (XRD). The results confirmed that PVBTA-TFSI is chemically stable against LPSCl. Furthermore, the thermal stability of PVBTA-TFSI was measured by TGA, as shown in Figure 9. The decomposition temperature of PVBTA-TFSI is about 365°C, with most of the decomposition occurring between about 400°C and 600°C, which is much higher than the temperature (150°C) applied to coatings.

[0060] The specific surface areas of the coated and untreated NCMs are evaluated using the Brunauer-Emmett-Teller (BET) model. For example, the specific surface areas of untreated NCM, 5P-NCM, and 1P-NCM are 0.593 m, respectively. 2 / g, 0.291m 2 / g, and 0.412m 2 The surface area of ​​the NCM particles is 1 / g. While SEM observations reveal little difference in particle aggregation between untreated and polymer-coated NCMs, BET measurements show a decrease in surface area with increasing coating weight percentage. This may be due to the increased polymer aggregation. TEM images were recorded in bright-field to enhance the contrast between the coating layer and the NCM particles. For one example of the present invention (presented in Figure 10), as shown in Figure 10 ((a) untreated NCM, (b) 1P-NCM, (c) 5P-NCM), all observed particles are uniformly coated with a homogeneous coating layer, although there is slight variation in thickness. 1P-NCM has a uniform coating of approximately 4 nm, while 5P-NCM has a much thicker coating of approximately 10 nm.

[0061] To characterize the composition and distribution of the coating more precisely, ToF-SIMS is implemented as a surface-sensitive technique with high lateral resolution (<50 nm). To chemically identify the coating on the NCM particle structure, pressed PVBTA-TFSI powder is measured as a reference material. Due to collision cascades initiated by the high-energy analytical beam, CHOF is detected during the ToF-SIMS measurement with adequate signal intensity. - , S.N.O. - , CF3 - These fragments are also formed in the coated sample, confirming the presence of a PVBTA-TFSI coating on the NCM particles.

[0062] Overall, considering the SEM, TEM, and ToF-SIMS results, the microstructure of the PVBTA-TFSI coating can be defined as follows: The coating is uniformly distributed and completely covers the NCM particles. The thickness of the 1 wt. % coating is approximately 4 nm, while the 5 wt. % coating is thicker (approximately 10 nm). In certain embodiments, the coating has localized polymer agglomerates on the surface, e.g., 40-100 nm thick (observed in the 10 nm thick 5 wt. % coating example; those skilled in the art will appreciate that localized polymer agglomerates vary with the average thickness and have corresponding sizes). Based on these analytical results, both the 1 wt. % and 5 wt. % coatings effectively prevent direct physical contact between the CAM and the SSE, thereby stabilizing the interface.

[0063] <Electrochemical property evaluation> <Rate characteristic test> The performance of the coated cathode is defined and evaluated by its rate capability and cycling stability compared to that of the untreated NCM. Different C-rate performances were investigated to elucidate the rate capability, as shown in Figure 11(a). Initially, the PVBTA-TFSI-coated NCM did not perform better than the untreated NCM. However, at 0.5C and 1C rates, the performance of the 1 wt% coated NCM was improved, and the 5 wt% coated NCM cell exhibited comparable capacity to the untreated NCM cell. Without being bound by any particular theory, the superior rate capability of the 1 wt% coated NCM at 0.5C and 1C rates may be due to the protection of the polymer coating after several cycles. Furthermore, at the 25th cycle, the coated NCM exhibited better reversibility in the discharge process, as shown in Figure 12(b). Figure 11(b) shows the first charge cycle at 2V to 3V (vs. Li). +Figure 12(a) shows the differentially expanded galvanostatic charge and discharge profiles of the coated cell (Li-In / Li-In). The current decreases with increasing polymer content. This indicates that the polymer protects the electrode from electrochemical degradation at the unstable interface between the electrode and electrolyte, and this effect is mainly evident in the first cycle. However, as shown in Figure 12(a), the protective layer in the coated cell reduces the current by approximately 3 V (vs. Li) in the first cycle compared to the untreated cell. + / Li-In) produces a larger overvoltage.

[0064] To observe the effect of the PVBTA-TFSI coating on the battery performance, galvanostatic cycling was performed at 0.1 C (Fig. 4(a)) and 0.25 C (Fig. 4(d)) for the 5P-NCM, 1P-NCM, and untreated NCM cells, respectively. During cycling, the current was 0.1 C, 3.15 V (vs. Li) for a specific number of cycles. + / Li-In) and EIS test is performed at 3.15V (vs. Li + The potential of 1000mV / Li-In is chosen to achieve a sufficiently high lithium diffusion coefficient and the lowest charge transfer resistance (R ct ) is chosen to ensure that the impedance of the layered oxide cathode material is stable. Furthermore, the impedance of the layered oxide cathode material depends on the state of charge of the electrode, so impedance measurements at a fixed potential are necessary. CA is used immediately before EIS measurements to ensure that the impedance measurements are performed at a sufficiently steady state. The cell voltage is maintained at 3.15 V (vs. Li) until the current drops below 1%. + This stabilizes the Li atoms that diffuse into the CAM particles. + can balance the lithium concentration in the NCM particles. In addition, a 2-hour relaxation time was allowed after each charge and discharge process to calculate the active mass. V OC Record the following.

[0065] Regarding the 0.1C cycling performance (Figure 4(a)), 1P-NCM exhibited the highest capacity retention rate of approximately 86%, while 5P-NCM exhibited a capacity retention rate of approximately 75.3%. However, the capacity retention rate of the untreated NCM was only approximately 70.4%. These results are consistent with the 0.25C cycling performance (Figure 4(d)), confirming that 1P-NCM significantly improves the long-term cycling stability of NCM in SSB. However, not all polymers can be used as protective layers while maintaining a high capacity of approximately 180 mAh / g. While not being limited to a particular theory, it is likely that strong intermolecular interactions and interactions with the cathode material are required. Furthermore, the counterion of the polycation, TFSI, - It is believed that this aids in lithium ion conduction in the thin coating layer. The coating layer does not inherently contain lithium, but can acquire the small amount of lithium ions necessary for lithium ion conduction from the electrolyte or cathode material. Therefore, it is within the scope of the present invention for the polyelectrolyte polymer to be a polycationic polymer, a polyanionic polymer, a zwitterionic polymer, a polymer in which a polycation is complexed with a polyanion, or a mixture of any two or more of the foregoing polyelectrolyte polymers. The range of lithium ion conductivities that can be used in the polymer coatings of the present invention is very broad, because the thickness of the polymer coating is very thin, preferably less than 100 nm, so low ionic conductivity is not a disadvantage.

[0066] Without being bound by any particular theory, the improved cycling performance of the SSB according to the present invention may be due to several reasons. First, the active mass (the amount of active material actually utilized) of the cathode material can be more effectively utilized due to the reduction of contact loss and electrochemically inactive interfacial layer between the active material and the electrolyte. Interfacial decomposition between the active material and the electrolyte includes chemical, electrochemical, and chemomechanical degradation. Interfacial decomposition can result in the formation of an electrochemically inactive surface or a highly resistive layer. Furthermore, the electrochemically inactive surface layer and chemomechanical shrinkage can cause the loss of contact between the NCM and the solid electrolyte, resulting in a decrease in R in the impedance spectrum.ct Another reason for the improvement achieved by the present invention may be due to the mitigation of the increase in the lithium diffusion path length, which can be increased by the aforementioned volume changes, contact loss, and particle cracking caused by interfacial decomposition.

[0067] <Contact loss and electrochemically inert interface layer> To quantify and analyze contact losses and the electrochemically inactive cathode / electrolyte interfacial layer, the active mass of the cell is measured during operation using methods well known to those skilled in the art. Experimental results are shown in Figure 4(b), which represents an exemplary measurement at 0.1 C, and Figure 15, which represents an exemplary measurement at 0.25 C. Briefly, a cell consisting of a fixed potential NCM cathode and an In / InLi anode is charged at an equilibrium open circuit potential (V OC ) This V OC follows a well-defined function of the state of charge, which represents the lithium content (Li_X) of the NCM. V vs. Li_X OC Using the reference data of the function (Fig. 14), the actual specific capacity (Q act ) can then be calculated from the measured discharge capacity (Q meas ) and Q act From the above, the active mass (m act ) can be calculated.

[0068]

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[0069] In Fig. 4(b), the m of the polymer-coated NCM cell and the untreated NCM cell in the 0.1C cycle test act First, the m of 1P-NCM, 5P-NCM, and untreated NCM cells were compared. actThe active masses of the polymer-coated NCM cells were approximately 7.6 mg, 7.4 mg, and 7.8 mg, respectively. The active mass of the polymer-coated NCM cells was slightly lower than that of the untreated NCM cells because some of the polymer coating on the NCM was too thick, insulating the NCM. However, after 100 cycles at a 0.1 C rate, the active masses of the untreated, 1P-NCM, and 5P-NCM cells were significantly higher than those of the untreated, 1P-NCM, and 5P-NCM cells. act The retention rates are approximately 81.1%, 92%, and 85.5%, respectively. act Without being bound by any particular theory, the higher retention rate can be explained by the reduction of the electrochemically inactive interfacial layer. However, the polymer coating of 5P-NCM is thicker, which hinders ion or charge transport to some extent, so 1P-NCM exhibits a lower retention rate than 5P-NCM. act High retention. The data shown demonstrates the best results to date at thicknesses of 4 nm to 5 nm, but these results should not be interpreted as limiting the thickness range. Depending on the ionic conductivity of the polyelectrolyte (e.g., polycationic polymer), the coating thickness can be varied from 0.1 nm to 1000 nm. Similar results can be observed in 0.25C cycling tests (Figure 15).

[0070] For example, as shown in Figure 4(c), 0.1 C EIS measurements were performed during cycling, and exemplary results are shown in Figure 16. The cathode-solid electrolyte interface provides information about contact loss and interface degradation, and R ct This is an important factor affecting the + In the first cycle of the ion exchange reaction (I / Li-In), the thicker the polymer coating layer, the higher the R ct The m act However, after 100 cycles, the R of the untreated NCM cell ct is the R of the 1P-NCM and 5P-NCM cells ct The R of the untreated NCM cell is significantly higher than that of the untreated NCM cell (173 Ω, 1P-NCM: 115.1 Ω, 5P-NCM: 106.9 Ω). ctWithout being bound to any particular theory, the significant increase in m may be due to severe contact loss and interfacial degradation. EIS measurements indicate that the polymer coating acts as a protective layer at the NCM / LPSCl interface, act This is consistent with the results of the calculation and the discussion of dQ / dV. Furthermore, the 1P-NCM and 5P-NCM cells showed a R ct The results are comparable, indicating that a 1 wt% polymer coating is sufficient to act as a protective layer for the NCM. EIS measurements of the 0.25C cycled cell (see, for example, Figure 3) also show similar conclusions to those of the 0.1C results.

[0071] <Lithium diffusion pathways within the cathode composite> The lithium diffusion path length within the cathode composite is expected to increase during cycling due to contact loss, interfacial degradation, and cracking of NCM particles. The Warburg behavior in EIS is fitted by a particle size distribution (EIS-PSD) model, as known to those skilled in the art, to determine the lithium diffusion path length within the cathode composite. In general, ideal finite-space Warburg behavior describes diffusion throughout the entire sample volume, including the ion blocking boundary in the current collector and the innermost core of the NCM. When the frequency is low enough to reach the blocking boundary, the impedance exhibits capacitive-like behavior, with a continuous change from 45° to 90° in the Nyquist plot. Therefore, to obtain the finite-space Warburg behavior in EIS, the lower cutoff frequency is set to 100 μHz. Finite-space Warburg impedance element for cylindrical particles:

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[0072]

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[0073] Equation 4 is used to fit the finite spatial diffusion tail of the EIS in combination with the transition line model (TLM), as is well known in the art. C diff is the total differential capacitance of the entire electrode (C diff =∂Q / ∂E), and 340mAhV -1 g -1 (3.15V (vs. Li + / Li-In), and x = 0.6) are assumed and calculated from the reference data (Figure 14).

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[0074] To compare the lithium transport in NCM particles after the cycle test, the diffusion coefficient was measured after 100 cycles of the 0.1C test.

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[0075] V0 is the open circuit potential V of the previous cycle OC C0 is the equilibrium concentration, i.e., the lithium concentration before the polarization step. Z w is calculated by EIS after each relaxation process. Re is the Warburg coefficient determined from the ω vs. data. W is expressed as W=∂In(a i ) / ∂In(c i), which means that the activity gradient is related to the concentration gradient when only one ionic and electronic species are considered. Furthermore, n, F, and A are the number of transferred electrons, Faraday's constant, and electrochemically active electrode surface, respectively. Because the contact between the NCM and the electrolyte may be lost during cycling, the electrochemically active electrode surface A after cycling was estimated as A = (BET area of ​​NCM) × (active mass after cycling) / (active mass before cycling). As supporting evidence, W can be determined from GITT experiments using equation [5]. Therefore,

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[0076] As can be seen from Figure 18(b), after 100 cycles, the untreated NCM cell

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[0077] <Morphology and interface stability after cycling> Low-angle FIB-SEM was utilized to observe the morphological changes in the cathode composites after cycling. The untreated NCM cell exhibited more cracks within the particles than the coated NCM cell, while the 5P-NCM cell exhibited the least cracks. Without being bound by any particular theory, one reason for the reduced cracking may be due to less lithium extraction from the NCM, especially due to the H2 + H3 phase transition during the charging process, where the most severe volume change occurs. However, as shown in Figure 12(a), the capacity and the 4.1 V (vs. Li + The area under the dQ / dV plot, which is higher than the dQ / dV (dQ / Li), is comparable for both the polymer-coated and untreated NCM cells, indicating that the H2+H3 phase transition process is similar in all NCM cells. Therefore, the reduction in cracking in the coated NCM is due to the polymer reducing the volume expansion and contraction of the NCM cathode material during cycling. To optimize this effect, the coating thickness must be increased. Because increasing the coating thickness decreases electrical conductivity, there is an optimum coating thickness, which ranges from 0.1 nm to 1000 nm. The optimal coating thicknesses that have been tested so far are typically in the range of approximately 4 nm to approximately 5 nm.

[0078] The comparative ToF-SIMS experiments disclosed herein between untreated and coated NCM demonstrate the reduction in electrolyte decomposition products, thereby demonstrating the favorable impact of the present invention on the electrochemical cycling stability of electrode active materials, particularly cathode active materials, in combination with an electrolyte. Those skilled in the art will know how to perform such comparative ToF-SIMS measurements, for example, how to set the following experimental parameters: - the number of cycles of the electrochemical cell to be performed before disassembly and investigation (e.g., up to several hundred cycles); - selection of the decomposition processes to be considered (for example processes between the current collector and the solid electrolyte, and / or between the carbon additive and the solid electrolyte, and / or between the CAM (i.e. the coating according to the invention) and the solid electrolyte); -Selection of indicator molecules to indicate oxidative degradation, e.g., phosphate (PO x - ); -Selection of appropriate parameters to provide sufficient statistical confidence in the experimental results (e.g., measuring 10 or more spectra per sample).

[0079] The experimental results are as follows: -PO coated sample x - (Especially PO - , PO2 - , PO3 - The amount of phosphate was significantly reduced, demonstrating that the exemplary 1 wt. % and 5 wt. % PVBTA-TFSI coatings tested effectively reduced the formation of phosphate. Thus, the decomposition of thiophosphate-based solid electrolytes is inhibited by the exemplary PVBTA-TFSI coatings tested. At 1 wt. %, no detectable PO2 - and PO3 - The fragments were more than 5 wt % coating, proving that thicker coatings are more effective than thinner coatings in inhibiting the decomposition of the solid electrolyte. [Brief explanation of the drawings]

[0080] [Figure 1]FIG. 1 is an exemplary schematic diagram of the synthesis of PVBTA-TFSI and the spray coating process of NCM particles with PVBTA-TFSI. [Figure 2A] This is an exemplary schematic diagram of electrochemical analysis. The charge process is indicated by solid arrows, and the discharge process is indicated by dotted arrows. The ASSB was charged at a constant current to 3.15 V (vs. Li+ / Li-In), and then the potential was maintained at 3.15 V (vs. Li+ / Li-In) until the current dropped to less than 1%. EIS measurements were then performed at frequencies from 1 MHz to 100 μHz. The ASSB was then charged at a constant current to 3.7 V (vs. Li+ / Li-In), followed by a two-hour relaxation period. Finally, the ASSB was discharged to 3.7 V (vs. Li+ / Li-In) and a two-hour relaxation period. [Figure 2B] For clarity, it should be noted that the inset graph in the first (main) part of Figure 2A has been duplicated, enlarged, and redrawn following the first part of Figure 2A, and the correlation between the enlarged copy of the inset graph and the inset graph can be easily recognized by the progression of the plotted values ​​or curves. [Figure 2C] For clarity, it should be noted that the inset graph in the first (main) part of Figure 2A has been duplicated, enlarged, and redrawn following the first part of Figure 2A, and the correlation between the enlarged copy of the inset graph and the inset graph can be easily recognized by the progression of the plotted values ​​or curves. [Figure 3] FIG. 1 illustrates the EIS of 1P-NCM, 5P-NCM, and untreated NCM cells, each measured at 0.25 C after chronoamperometry. [Figure 4A] FIG. 1(a) is a graph illustrating the long-term cycle characteristics at 0.1C. [Figure 4B] (b) Graph illustrating the long-term cycling characteristics with corresponding active mass change at 0.1C. [Figure 4C] (c) A graph illustrating the long-term cycle characteristics in the Nyquist plots (measured at 0.1 C) at the 1st and 100th cycles. [Figure 4D](d) A graph illustrating the long-term cycle characteristics at 0.25C. [Figure 5] Figure 1 illustrates the H NMR spectrum of PVBTATFSI (400 MHz, deuterated acetone): δ 1.36–1.99 (H1, H2), δ 2.05 (acetone-d6), δ 3.14 (H6), δ 4.4–4.9 (H5), δ 6.5–7.4 (H3, H4). [Figure 6] Figure 1 illustrates the FT-IR spectra of PVBTA-TFSI, PBVTA-Cl, and LiTFSI. FT-IR (cm-1) of PVBTA-TFSI: 973 (CN stretching), 1346, 1326, 1176, 1132, 1050 (TFSI-), 1612, 1480, 1422 (aromatic C=C stretching), 3043, 2922, 2852 (alkyl C-H stretching), 3400 (HO). FT-IR (cm-1) of PVBTA-Cl: 973 (CN stretching), 1612, 1480, 1422 (aromatic C=C stretching), 3015, 2922, 2852 (alkyl C-H stretching), 3400 (HO). FT-IR of LiTFSI (cm-1): 1327 (SO2 asymmetric stretching), 1245 (CF3 symmetric stretching), 1204 (CF3 asymmetric stretching), 1147 (SO2 symmetric stretching), 1065 (asymmetric S2N stretching). [Figure 7] 1 illustrates XRD measurements of LiTFSI and LiTFSI, demonstrating that PVBTA-TFSI is an amorphous polymer. [Figure 8A] Figure 1 illustrates the IR spectrum: FT-IR of PVBTATFSI mixed with LPSCL shows no difference before and after heating. [Figure 8B] FIG. 1 illustrates the XRD pattern of PVBTATFSI mixed with LPSCL after heating, which is in perfect agreement with the peaks before heating. [Figure 9] FIG. 1 is a TGA analysis of PVBTA-TFSI (air / O 2 , heating rate 10° C. / sec) showing an example of the upper temperature limit for spray drying. [Figure 10]1 shows exemplary TEM images of (a) untreated NCM, (b) 1P-NCM, and (c) 5P-NCM. TEM (and ToF-SIMS evaluation, data not shown) confirm a homogeneous PVBTA-TFSI coating that completely covers the NCM CAM (i.e., NCM particle, illustratively the coating). [Figure 11A] FIG. 1 shows (a) an exemplary comparison of rate performance tests. [Figure 11B] (b) An exemplary comparison of differential capacity plots at 1 cycle at 0.1 C, zoomed in at 2-3 V (vs. Li+ / Li−In). The inset shows the capacity and coulombic efficiency at different C-rates for coated and untreated NCM cells at 25 cycles at 0.1 C. [Figure 11C] The inset in part (b) is an additional enlarged drawing separate from part (b) for ease of reading. [Figure 12] FIG. 1 shows an exemplary comparison of differential capacity plots for polymer-coated and untreated NCM cells at (a) 1 cycle at 0.1 C and (b) 25 cycles at 0.1 C. [Figure 13] 1 shows an exemplary comparison of 0.1C cycling stability of untreated NCM, 5P-NCM, and 5 wt% PVP-coated NCM (the first is untreated NCM and the last is PVP-coated NCM, which are comparative examples according to the prior art). The 5P-NCM and the 5 wt% PVP-coated NCM have similar capacity retention, but different initial capacities. As is well known in the prior art, the capacity retention is highly dependent on the initial capacity. As the initial capacity increases, the capacity retention rapidly decreases. Therefore, the fact that the capacity retention is similar between the 5P-NCM (according to the present invention) and the 5 wt% PVP-coated NCM (prior art) despite the different initial retentions is an unexpected and surprising effect of improving the capacity retention. [Figure 14]1 shows an exemplary relationship between x and VOC in LixNi0.83Mn0.06Co0.11O2, obtained by constant current charging and discharging a liquid lithium-ion battery at 0.02 C. VOC was obtained by charging or discharging every 20 minutes followed by a 2-hour relaxation period. Furthermore, x in LixNi0.83Mn0.06Co0.11O2 can be calculated from the current and time. [Figure 15] 10 is a graph showing an exemplary comparison of corresponding active mass changes in 0.25C cycling tests. [Figure 16] 1 is a table of exemplary data from EIS measurements. [Figure 17] FIG. 1 shows an exemplary variation of the lithium diffusion path length Ldiff from (a) EIS-PSD model and (b) CA measurements. [Figure 18] (a) Warburg coefficient (Zw) determined by EIS, and (b) diffusion coefficient measured by the GITT method.

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Claims

1. i) a plurality of core particles, each core particle comprising at least one compound of formula (I): Li １＋ｗ [Ni １－ｘ－ｙ－ｚ Co ｘ Mn ｙ M ｚ ] １－ｗ O ２ (I) and / or at least one compound of formula (II) Li １＋ｗ [Ni １－ｘ－ｙ－ｚ Co ｘ Al ｙ M ｚ ] １－ｗ O ２ (II) and / or LiNiO ２ (Wherein, 0≦w≦0.3, 0≦x≦1, 0≦y≦1, 0≦z≦0.25, 0<x+y+z<1, M is at least one chemical element independently selected from the list of chemical elements including Be, Mg, Sr, Ba, Al, Ga, In, Tl, and transition metals other than Ni, Co, and Mn. a plurality of core particles comprising: ii) the surface of said core particles exhibiting a coating comprising at least one polycationic organic polymer or at least one polyanionic organic polymer with at least one counter anion; Including, A coated particle material, wherein the coating covers at least 50% of the surface of the core particle.

2. 2. The coated particle material of claim 1, 1. A coated particulate material, characterized in that the plurality of core particles according to feature i) of claim 1 already comprise a first coating, whereby the coating according to feature ii) of claim 1 forms an outer (second) coating of the coated particulate material, and the first coating forms an inner coating of the coated particulate material.

3. 3. The coated particle material according to claim 1 or 2, The at least one polycationic organic polymer is selected from the group consisting of poly((4-vinylbenzyl)trimethylammonium), poly((3-vinylbenzyl)trimethylammonium), poly((2-vinylbenzyl)trimethylammonium), poly((2-vinylbenzyl)trialkylammonium), poly((2-vinylbenzyl)triarylammonium), poly((2-vinylbenzyl)alkylarylammonium), poly((3-vinylbenzyl)trialkylammonium), poly((3-vinylbenzyl)triarylammonium), poly((3-vinylbenzyl)alkylarylammonium), poly((4-vinylbenzyl)trialkyl ammonium), poly((4-vinylbenzyl)triarylammonium), poly((4-vinylbenzyl)alkylarylammonium), protonated polyaniline, protonated chitosan, protonated polypyrrole, protonated polydiallyldimethylamine, protonated polyethyleneimine, protonated polythiophene, oxidized polyaniline, oxidized chitosan, oxidized polypyrrole, oxidized polydiallyldimethylamine, oxidized polyethyleneimine, oxidized polythiophene, poly(diallyldimethylammonium), poly(allylammonium), poly(1-alkyl-3-vinylimidazolium), or The at least one polyanionic organic polymer may be selected from the group consisting of poly(acrylic acid), graphene oxide, polysaccharide gums such as xanthan gum, poly(vinyl alcohol), polydopamine, chitosan, poly(styrene sulfonate), poly(3,4-ethylenedioxythiophene) / polystyrene sulfonate, sulfonated polyphenylene sulfone, copolymers with sulfonated polyphenylene sulfone, sulfonated poly(2,6-dimethyl-1,4-phenylene oxide), poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)isothiazolinone], ... imide], poly[(4-styrenesulfonyl)(trifluoromethyl(S-trifluoromethylsulfonylimino)sulfonyl)imide], sulfonated polymers such as poly(ether ether ketone), poly(3-sulfopropyl methacrylate), and poly[(4-styrenesulfonyl)(fluorosulfonyl)imide], phosphonated polymers such as poly(vinylphosphonic acid), polyphosphonates, poly([2-(methacryloyloxy)ethyl]phosphate), A coated particle material characterized by:

4. 4. The coated particle material according to claim 1, the at least one polycationic organic polymer or the at least one polyanionic organic polymer is combined with at least one neutral polymer having at least one amide group; The at least one neutral polymer having at least one amide group is independently selected from the list comprising polyvinylpyrrolidone, poly(N-vinylformamide), polyamide. A coated particle material characterized by:

5. 5. The coated particle material according to claim 1, The at least one counter anion of the polycationic polymer is selected from the group consisting of fluoride, chloride, bromide, sulfate, bis(trifluoromethanesulfonyl)imide, tetrafluoroborate, nitrate, hexafluorophosphate, thiocyanate, bis(fluorosulfonyl)imide, azide, borate, BO ３ ３－ , B ２ O ５ ４－ , B ４ O ５ (OH) ４ ２－ , B ４ O ７ ２－ independently selected from a list including or The at least one counter cation of the polyanionic polymer is selected from the group consisting of aluminum (III), barium (II), beryllium (II), calcium (II), chromium (III), copper (I), copper (II), gold (I), gold (III), hydrogen (I), iron (II), iron (III), lead (II), lead (IV), lithium (I), magnesium (II), manganese (II), manganese (III), manganese (IV), mercury (II), potassium (I), silver (I), sodium (I), strontium (II), tin (II), tin (IV), zinc (II), polyatomic cations, ammonium, H ＋ , mercury (I), Li ＋ Na ＋ K ＋ Ca ２＋ Mg ２＋ Al ３＋ Polyatomic cations, NH ４ ＋ , ammonium derivatives, NR ３ H ＋ , N.R. ２ H ２ ＋ , N.R.H. ３ ＋ wherein R is independently selected from the list comprising alkyl, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl. A coated particle material characterized by:

6. 6. The coated particle material according to claim 1, The average thickness of the coating comprising the at least one polycationic organic polymer or the at least one polyanionic organic polymer is in the range of 0.1 nm to 100 nm, preferably 1 nm to 10 nm, and most preferably 2 nm to 5 nm. A coated particle material characterized by:

7. 7. The coated particle material of claim 6, the thickness of the coating comprising the at least one polycationic organic polymer or the at least one polyanionic organic polymer has, in at least one region, a deviation from the average thickness value of up to +1000% of the average thickness value and / or up to -80% of the average thickness value, The at least one region in which the coating thickness has a deviation from the average value is defined by at least one measurement point. A coated particle material characterized by:

8. A method for preparing a coated particle material according to any one of claims 1 to 7, characterized in that it comprises the following steps: a) providing a plurality of core particles according to feature i); b) coating the plurality of core particles prepared according to step a) with at least one polycationic organic polymer, or at least one polyanionic polymer, or a combination of at least one polycationic polymer and at least one neutral polymer, or a combination of at least one polyanionic polymer and at least one neutral polymer.

9. 9. The method of claim 8, Step b) is 1) providing or synthesizing at least one polycationic organic polymer, or at least one polyanionic organic polymer, or a combination of at least one polycationic polymer and at least one neutral polymer, or a combination of at least one polyanionic polymer and at least one neutral polymer; 2) preparing a solution of at least one polycationic organic polymer, or at least one polyanionic organic polymer, or a combination of at least one polycationic polymer and at least one neutral polymer, or a combination of at least one polyanionic polymer and at least one neutral polymer, prepared or synthesized in step 1), in a solvent suitable for spray drying, wherein the solvent suitable for spray drying is a polar aprotic solvent having a boiling point below 200°C; 3) coating the plurality of core particles prepared according to step a) with the solution of at least one polycationic polymer, or at least one polyanionic polymer, or a combination of at least one polycationic polymer and at least one neutral polymer, or a combination of at least one polyanionic polymer and at least one neutral polymer, prepared according to step 2) by spray drying. A method comprising:

10. 1. An electrode for use in a lithium ion battery, comprising: At least one coated particulate material according to any one of claims 1 to 7; at least one lithium ion conducting solid electrolyte, and / or at least one lithium ion conducting liquid electrolyte, and / or at least one lithium ion conducting polymer electrolyte; at least one conductive component; Including, an electrode, wherein the at least one conductive component is independently selected from the list comprising carbon black, graphite, graphene, carbon fullerenes, and carbon nanotubes.

11. 11. The electrode of claim 10, An electrode characterized in that it contains one or more binders.

12. A coated particle material according to any one of claims 1 to 7 and / or an electrode according to claim 10 or 11; At least one solid electrolyte; Including, The at least one solid electrolyte is Li ６ P.S. ５ Cl, Li ７＋ｏ－ｐ M ＩＶ ｏ M Ｖ １－ｏ Ch ６－ｐ X ｐ , Li １＋ｍ Al ｍ Ti ２－ｍ (P.O. ４ ) ３ , Li ７ La ３ Zr ２ O １２ , Li ３ｎ La ２／３－ｎ TiO ３ , Li １０ GeP ２ S １２ (In the formula, M ＩＶ are independently selected from the list including Si, Ge, and Sn; M Ｖ are independently selected from the list including P, Sb, Ch are independently selected from the list including O, S, Se, and X is Cl, Br, I, BH ４ and wherein 0<m≦1, 0<n≦0.3, 0≦o≦1, 0≦p≦2.

13. A coated particle material according to any one of claims 1 to 7 and / or an electrode according to claim 10 or 11; at least one liquid electrolyte; Including, the at least one liquid electrolyte comprises at least one lithium salt dissolved in an aprotic solvent or a mixture of at least two aprotic solvents; 10. A lithium ion battery, wherein the at least one aprotic solvent is independently selected from the list of aprotic solvents including ethylene carbonate, diethyl carbonate, dimethyl carbonate, propylene carbonate, fluoroethylene carbonate, dioxolane, dimethylformamide.

14. A coated particle material according to any one of claims 1 to 7 and / or an electrode according to claim 10 or 11; at least one polyelectrolyte; Including, the at least one polyelectrolyte comprises at least one polymer independently selected from the list of polymers comprising polyethylene glycol, acrylate polymer, poly(methyl methacrylate), polyvinylpyrrolidone, polyacrylonitrile; the at least one polymer is crosslinked or non-crosslinked; and / or a lithium ion battery, wherein said at least one polymer is a homopolymer or a copolymer.

15. A coated particle material according to any one of claims 1 to 7 and / or an electrode according to claim 10 or 11; a polymer electrolyte comprising polyethylene oxide, wherein the polyethylene oxide comprises at least one lithium salt or at least one single ion conductor; Including lithium-ion batteries.

16. 15. The lithium ion battery according to claim 13 or 14, 1. A lithium-ion battery, characterized in that the at least one polymer electrolyte comprises at least one plasticizer, and / or at least one ionic liquid, and / or at least one liquid electrolyte.

17. Use of the coated particulate material according to any one of claims 1 to 7, Preparation of the electrode according to claim 10 or 11, or Preparation of the lithium ion battery according to any one of claims 12 to 16. For use.

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