Solid-state electrolyte particle and preparation method therefor, solid-state electrolyte, semi-solid-state electrolyte, positive electrode, battery, and electric device

Abstract

Provided is a solid-state electrolyte particle, comprising a compound represented by the following general formula: Lia(Mb)XcX'd, wherein M is a metal element, X is selected as Cl, X' comprises one or more of F ion, I ion, Br ion, N ion, P ion, S ion, CN-, oxygen-containing anion, and pseudohalide anion, 0.5<a<5, 0.2<b<2, c+d*ε1=a+b*ε2, ε1 is the weighted average valence of X', and ε2 is the weighted average valence of element M. The present application also relates to a preparation method for the solid-state electrolyte particle, and a solid-state electrolyte, a semi-solid-state electrolyte, a positive electrode, a battery, and an electric device comprising the solid-state electrolyte particle.

Description

Solid electrolyte particles and preparation method thereof, solid electrolyte, semi-solid electrolyte, positive electrode, battery and electrical device

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to a Chinese patent application filed with the Patent Office of China on January 3, 2024, with application number 202410007598.0 and application name “A solid electrolyte particle and its preparation method, solid electrolyte, semi-solid electrolyte, positive electrode, battery and electrical device”, the entire contents of which are incorporated by reference into this application. Technical Field

[0003] The present invention belongs to the technical field of solid-state batteries, and specifically relates to solid electrolyte particles and a preparation method thereof, a solid electrolyte, a semi-solid electrolyte, a positive electrode, a battery and an electrical device. Background Art

[0004] Currently, solid-state batteries have become a hot topic in the research field of energy storage devices such as lithium batteries and sodium batteries due to their high energy density and excellent safety. Solid-state electrolytes are a key component of solid-state batteries. In addition to traditional inorganic solid-state electrolyte materials, halogen solid-state electrolytes have become a new research focus due to their unique chemical and physical properties. Halogen solid-state electrolytes generally have good ionic conductivity and stable chemical properties, making them potential applications in the field of high-performance batteries. In particular, halogen electrolytes have shown excellent interfacial stability and high electrical conductivity in lithium batteries and other solid-state battery systems.

[0005] Current halogen-based solid electrolytes face compatibility issues with lithium metal anodes. Common halogen-based solid electrolytes, such as Li3InCl6 and Li3YCl6, are prone to interfacial reactions when in contact with lithium metal anodes, resulting in the formation of byproducts and degrading battery performance.

[0006] Summary of the Invention

[0007] In response to the problem of interface side reactions between existing halogen solid electrolytes and negative electrodes, the present invention provides a solid electrolyte particle and a preparation method thereof, a solid electrolyte, a semi-solid electrolyte, a positive electrode, a battery and an electrical device.

[0008] The technical solutions adopted by the present invention to solve the above technical problems are as follows:

[0009] In one aspect, the present invention provides a solid electrolyte particle comprising a compound represented by the following general formula:

[0010] Li a (M b )X c X' d

[0011] Wherein, M is a metal element, X is selected from Cl, X' includes F ion, I ion, Br ion, N ion, P ion, S ion, CN - , one or more of oxygen-containing anions, and pseudohalide anions; 0.5<a<5, 0.2<b<2, c+d*ε1=a+b*ε2, ε1 is the weighted average valence of X', and ε2 is the weighted average valence of the M element.

[0012] Optionally, M includes one or more of Ga, Y, In, Mg, Sr, Sc, Al, Fe, Zr, Hf, Ta, Nb, W, Mn, Zn, Yb, Co, Mo, Sn, Ca, Pb, Ti, Ru and lanthanide metal elements.

[0013] Optionally, the oxygen-containing anions include O 2- 、CO3 2- PO4 3- 、P2O7 4- and SO4 2- One or more of; the pseudohalide anion includes SCN - PF6 - NH2 - 、AlF4 - and BF4 - One or more of .

[0014] Optionally, the molar ratio of X' to the X element in the solid electrolyte particles as a whole is (0.005-200):1.

[0015] Optionally, from the inside of the solid electrolyte particle to the outer surface of the solid electrolyte particle, the compound Li a (M b )X c X' d The doping concentration of X' is consistent.

[0016] Optionally, from the inside of the solid electrolyte particle to the outer surface of the solid electrolyte particle, the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a continuous decreasing and / or gradient decreasing trend.

[0017] Optionally, from the inside of the solid electrolyte particle to the outer surface of the solid electrolyte particle, the compound Li a (M b )X c X' d The doping concentration of X' in the compound increases first and then decreases.a (M b )X c X' d The doping concentration of X' decreases first and then increases.

[0018] Optionally, from the inside of the solid electrolyte particle to the outer surface of the solid electrolyte particle, the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a trend of continuous and / or gradient increase.

[0019] Optionally, the solid electrolyte particles include a core and a shell, wherein the shell is located outside the core, and the compound Li a (M b )X c X' d The doping concentration of X' is greater than that of the compound Li in the core a (M b )X c X' d The doping concentration of X' in .

[0020] Optionally, the core compound Li a (M b )X c X' d The molar ratio of X' to X element is (0.005-200):1, and the shell compound Li a (M b )X c X' d The molar ratio of X' to X element is (0.006-201):1.

[0021] Optionally, along the direction from the core to the shell, the compound Li in the shell a (M b )X c X' d The doping concentration of X' in the graphite crystals increases continuously, and / or

[0022] The compound Li in the shell a (M b )X c X' d The doping concentration of X' is consistent, and / or

[0023] The compound Li in the core a (M b )X c X' dThe doping concentration of X' in the graphite crystals increases continuously, and / or

[0024] The compound Li in the core a (M b )X c X' d The doping concentration of X' is consistent.

[0025] Optionally, the number of the shell layers is multiple, and the multiple shell layers are stacked in sequence in a direction away from the core portion, and in the direction away from the core portion, the compound Li in the multiple shell layers is a (M b )X c X' d The doping concentration of X' increases successively.

[0026] Optionally, the thickness of the shell layer is 10 nm to 1 μm, and the ratio of the thickness of the shell layer to the radius of the core portion is 1:(200-2).

[0027] In another aspect, the present invention provides a method for preparing the solid electrolyte particles as described above, wherein LiX, MX and a raw material containing X' are used as raw materials and the solid electrolyte particles are prepared by grinding or solvent co-dissolution recrystallization.

[0028] Optional steps include:

[0029] The raw materials LiX and MX are mixed and then ground. During the grinding process, a raw material containing X' is added, and the feeding rate of the raw material containing X' is controlled to increase continuously and / or gradually, so that the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a trend of continuous and / or gradient increase.

[0030] Optionally, the grinding is ball milling, the ball-to-material ratio is 15:1 to 25:1, the ball milling time is 3 to 10 hours, and the ball milling speed is 400 to 600 rpm.

[0031] Optional steps include:

[0032] The raw materials LiX and MX are dissolved in an organic solvent, and then heated to evaporate the organic solvent to precipitate solid electrolyte particles. During the evaporation of the organic solvent, the feeding rate of the raw material containing X' is controlled to increase continuously and / or gradually, so that the compound Li a (M b )X cX' d The doping concentration of X' in the middle shows a trend of continuous and / or gradient increase.

[0033] Optionally, the organic solvent includes one or more of hexane, heptane, octane, kerosene, toluene, p-xylene, ethylbenzene, carbon disulfide, carbon tetrachloride, propylene chloride, hexyl bromide, chloroform and dichloromethane and isomers of the above substances.

[0034] Optionally, a hydrolysis inhibitor is added to the organic solvent, and the added mass of the hydrolysis inhibitor is 20% to 120% of the solid electrolyte particles. The hydrolysis inhibitor includes one or more of NH4Cl, I2, LiI or S.

[0035] Optionally, the precipitated solid electrolyte particles are filtered and dried, and the drying treatment includes one or more of vacuum heating treatment, rotary evaporation drying treatment, vacuum freeze drying treatment or microwave vacuum drying treatment.

[0036] In another aspect, the present invention provides a solid electrolyte comprising the solid electrolyte particles as described above.

[0037] In another aspect, the present invention provides a semi-solid electrolyte comprising an electrolyte and the solid electrolyte particles as described above.

[0038] In another aspect, the present invention provides a positive electrode comprising a positive electrode material layer, wherein the positive electrode material layer comprises a positive electrode active material and the solid electrolyte particles or the semi-solid electrolyte as described above.

[0039] Optionally, based on the total mass of the positive electrode material layer being 100%, the mass percentage of the positive electrode active material is 50% to 99%, and the mass percentage of the solid electrolyte particles is 0.5% to 49.5%.

[0040] In another aspect, the present invention provides a battery comprising a positive electrode, an electrolyte and a negative electrode, wherein the positive electrode is selected from the positive electrode described above, and / or the electrolyte is selected from the solid electrolyte described above.

[0041] In another aspect, the present invention provides an electrical device comprising the battery as described above.

[0042] According to the solid electrolyte particles provided by the present invention, X' is added to the halide solid electrolyte by doping, wherein X' can spontaneously react at the interface in contact with the negative electrode lithium element to form a SEI interface layer (solid electrolyte membrane) on the surface of the solid electrolyte particles. The main component of the SEI interface layer is an inorganic lithium salt, which has stable electrochemical properties and can block direct contact between the solid electrolyte particles and the negative electrode, thereby forming a protective effect on the solid electrolyte particles and avoiding performance degradation caused by continuous reaction between the negative electrode lithium and the solid electrolyte. In addition, the SEI interface layer rich in inorganic lithium salts has high mechanical strength, can improve the stability of the solid electrolyte particles, avoid pulverization, and is also beneficial to inhibiting the growth of negative electrode lithium dendrites, thereby improving the cycle life of the battery. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIG1 is a schematic structural diagram of a solid electrolyte particle provided by one embodiment of the present invention;

[0044] FIG2 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0045] FIG3 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0046] FIG4 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0047] FIG5 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0048] FIG6 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0049] FIG7 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0050] FIG8 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention;

[0051] FIG9 is a schematic structural diagram of solid electrolyte particles provided by another embodiment of the present invention. DETAILED DESCRIPTION

[0052] In order to make the technical problems, technical solutions and beneficial effects solved by the present invention more clearly understood, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0053] 1 , an embodiment of the present invention provides a solid electrolyte particle comprising a compound represented by the following general formula:

[0054] Li a(M b )X c X' d

[0055] Wherein, M is a metal element, X is selected from Cl, X' includes F ion, I ion, Br ion, N ion, P ion, S ion, CN - , one or more of oxygen-containing anions, and pseudohalide anions; 0.5<a<5, 0.2<b<2, c+d*ε1=a+b*ε2, ε1 is the weighted average valence of X', and ε2 is the weighted average valence of the M element.

[0056] X' is added to the halide solid electrolyte by doping, wherein X' can spontaneously react at the interface in contact with the negative electrode lithium element to form a SEI interface layer (solid electrolyte membrane) on the surface of the solid electrolyte particles. The main component of the SEI interface layer is inorganic lithium salt, which has stable electrochemical properties and can block direct contact between the solid electrolyte particles and the negative electrode, thus protecting the solid electrolyte particles and avoiding performance degradation caused by continuous reaction between the negative electrode lithium and the solid electrolyte. In addition, the SEI interface layer rich in inorganic lithium salt has high mechanical strength, which can improve the stability of the solid electrolyte particles, avoid pulverization, and is also beneficial to inhibit the growth of negative electrode lithium dendrites, thereby improving the cycle life of the battery.

[0057] In the description of the present invention, the term "weighted average valence" refers to the compound Li a (M b )X c X' d The weighted average valence of the same element in the complex. For example, when X' is selected from N ions, its weighted average valence is 3. When X' is selected from N ions and oxygen ions with equal coordination numbers, its weighted average valence is (3+2) / 2=2.5.

[0058] In some embodiments, M includes one or more of Ga, Y, In, Mg, Sr, Sc, Al, Fe, Zr, Hf, Ta, Nb, W, Mn, Zn, Yb, Co, Mo, Sn, Ca, Pb, Ti, Ru and lanthanide metal elements.

[0059] M element is compound Li a (M b )X c X' d When M is selected from the metal elements described above, a crystal structure with a large number of cation vacancies can be formed, thereby facilitating the conduction of lithium ions in the solid electrolyte particles and improving the ionic conductivity of the solid electrolyte particles.

[0060] In some embodiments, the entropy of the solid-state conductor system is increased by doping with two or more of Ga, Y, In, Mg, Sr, Sc, Al, Fe, Zr, Hf, Ta, Nb, W, Mn, Zn, Yb, Co, Mo, Sn, Ca, Pb, Ti, Ru and lanthanide metal elements to improve the ionic conductivity of the solid electrolyte particles.

[0061] In some embodiments, the halogen includes two or more of Cl, Br and I. The doping of multiple halogens causes anions to be mixed, allowing lithium ions to migrate through the energy band gaps formed by different anion radii, thereby facilitating the improvement of ion conduction efficiency.

[0062] In some embodiments, the oxyanion comprises O 2- 、CO3 2- PO4 3- 、P2O7 4- and SO4 2- One or more of; the pseudohalide anion includes SCN - PF6 - NH2 - 、AlF4 - and BF4 - One or more of .

[0063] The above X' has a similar ionic radius to the halogen X, and while forming the SEI interface layer, it can increase the doping of the substituted compound Li a (M b )X c X' d The structural stability of the solid electrolyte particles can be improved to avoid the problem of irreversible crystal structure transformation during the charge and discharge cycle.

[0064] In some embodiments, the molar ratio of X' to the X element in the solid electrolyte particles as a whole is (0.005-200):1.

[0065] When the molar ratio of X' to the X element in the solid electrolyte particles as a whole is within the above range, it is beneficial to promote the formation of the SEI interface film on the surface of the solid electrolyte particles.

[0066] In some embodiments, the molar ratio of X' to the X element in the solid electrolyte particles as a whole is (0.01-100):1. In some embodiments, the molar ratio of X' to the X element in the solid electrolyte particles as a whole is (0.1-10):1.

[0067] In some embodiments, in the solid electrolyte particles, the compound Li a (M b )X cX' d The mass percentage of is greater than or equal to 60%. In a preferred embodiment, in the solid electrolyte particles, the compound Li a (M b )X c X' d The mass percentage of is greater than or equal to 70%. In a more preferred embodiment, in the solid electrolyte particles, the compound Li a (M b )X c X' d The mass percentage of is greater than or equal to 80%. In a more preferred embodiment, in the solid electrolyte particles, the compound Li a (M b )X c X' d The mass percentage is greater than or equal to 90%.

[0068] As shown in FIG1 to FIG9, in different embodiments, the compound Li in different regions of the solid electrolyte particles a (M b )X c X' d The doping concentration of X' can be the same or different, and when the compound Li in different regions of the solid electrolyte particles a (M b )X c X' d When the doping concentration of X' is different, it can be regularly increasing, decreasing or irregularly distributed.

[0069] In FIG. 1 to FIG. 9 , in the doping concentration coordinate system of X′, the abscissa is the corresponding distance from the center position of the solid electrolyte particle, and the ordinate is the doping concentration of X′.

[0070] As shown in FIG1 , in some embodiments, the compound Li a (M b )X c X' d The doping concentration of X' is consistent.

[0071] As shown in FIG2 to FIG4, in some embodiments, the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a continuous decreasing and / or gradient decreasing trend.

[0072] In some embodiments, the solid electrolyte particle includes a core and a shell, wherein the shell is located outside the core, and the compound Li a (M b )X c X' d The doping concentration of X' is less than that of the compound Li in the core a (M b )X c X' d The doping concentration of X' in .

[0073] Specifically, in different embodiments, along the direction from the core to the shell, the compound Li in the shell a (M b )X c X' d The doping concentration of X' in the graphite crystals decreases continuously, and / or

[0074] The compound Li in the shell a (M b )X c X' d The doping concentration of X' is consistent, and / or

[0075] The compound Li in the core a (M b )X c X' d The doping concentration of X' in the graphite crystals decreases continuously, and / or

[0076] The compound Li in the core a (M b )X c X' d The doping concentration of X' is consistent.

[0077] As an example, as shown in FIG2 , the compound Li in the core of the solid electrolyte particle a (M b )X c X' d The doping concentration of X' in the shell is greater than that of the compound Li a (M b )X c X' d The doping concentration of X' in the core is Li a (M b )X c X' d The doping concentration of X' is consistent, and the compound Li in the shell a (M b )X c X' dThe doping concentration of X' is consistent.

[0078] As shown in FIG3 , the compound Li in the core of the solid electrolyte particle a (M b )X c X' d The doping concentration of X' in the shell is greater than that of the compound Li a (M b )X c X' d The doping concentration of X' in the core is Li a (M b )X c X' d The doping concentration of X' in the shell layer shows a continuous decreasing trend. a (M b )X c X' d The doping concentration of X' shows a continuous decreasing trend, and the slopes of the two decreasing curves are consistent.

[0079] As shown in FIG4 , the compound Li in the core of the solid electrolyte particle a (M b )X c X' d The doping concentration of X' in the shell is greater than that of the compound Li a (M b )X c X' d The doping concentration of X' in the core is Li a (M b )X c X' d The doping concentration of X' in the shell layer shows a continuous decreasing trend. a (M b )X c X' d The doping concentration of X' shows a continuous decreasing trend, and the slope of the decreasing curve in the core is greater than that in the shell.

[0080] As shown in FIG5 , in some embodiments, the compound Li a (M b )X c X' d The doping concentration of X' in the nanostructured layer increases first and then decreases.

[0081] As shown in FIG6 , in some embodiments, the compound Li a (Mb )X c X' d The doping concentration of X' decreases first and then increases.

[0082] As shown in Figures 7 to 9, in some embodiments, the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a trend of continuous and / or gradient increase.

[0083] The inventors conducted further research based on the solid electrolyte particles described above and found that even if the total doping concentration of the solid electrolyte particles is the same, different doping concentrations in different regions of the solid electrolyte particles will lead to differences in the application performance of the battery. Specifically, when the direction from the inside of the solid electrolyte particle to the outer surface of the solid electrolyte particle is from the inside of the solid electrolyte particle to the outer surface of the solid electrolyte particle, the compound Li a (M b )X c X' d When the X' doping concentration in the electrolyte shows a continuously increasing and / or gradient increasing trend, the resulting battery has the best service life. It is speculated that this is because excessive X' doping will continuously consume lithium ions, thereby adversely affecting the battery's cycle performance. By forming a solid electrolyte particle structure with a low internal X' doping amount and a high external X' doping amount, on the one hand, the formation of the SEI interface film on the surface of the solid electrolyte particles and the structural stability of the SEI interface film are guaranteed; on the other hand, the overall doping concentration is reduced. Without sacrificing the high ionic conductivity of the core region, the surface gradient structure enhances stability, allowing the electrolyte to maintain high electrochemical performance during long-term charge and discharge cycles.

[0084] In some embodiments, the solid electrolyte particle includes a core and a shell, wherein the shell is located outside the core, and the compound Li a (M b )X c X' d The doping concentration of X' is greater than that of the compound Li in the core a (M b )X c X' d The doping concentration of X' in .

[0085] In some embodiments, the core compound Li a (M b )X c X' d The molar ratio of X' to X element is (0.005-200):1, and the shell compound Lia (M b )X c X' d The molar ratio of X' to X element is (0.006-201):1.

[0086] When the molar ratio of X' and X' elements in the core and shell of the solid electrolyte particles meets the above conditions, a relatively reasonable doping concentration distribution of the X' element is formed. After the solid electrolyte particle surface reacts with lithium to form the SEI interface film, the solid electrolyte particle can maintain its intact structure, which is beneficial to improving the battery cycle stability.

[0087] In some embodiments, along the direction from the core to the shell, the compound Li in the shell a (M b )X c X' d The doping concentration of X' in the graphite crystals increases continuously, and / or

[0088] The compound Li in the shell a (M b )X c X' d The doping concentration of X' is consistent, and / or

[0089] The compound Li in the core a (M b )X c X' d The doping concentration of X' in the graphite crystals increases continuously, and / or

[0090] The compound Li in the core a (M b )X c X' d The doping concentration of X' is consistent.

[0091] As an example, as shown in FIG7 , the compound Li in the core of the solid electrolyte particle a (M b )X c X' d The doping concentration of X' in the shell is less than that of the compound Li a (M b )X c X' d The doping concentration of X' in the core is Li a (M b )X c X' d The doping concentration of X' is consistent, and the compound Li in the shell a (M b )X cX' d The doping concentration of X' is consistent.

[0092] As shown in FIG8 , the compound Li in the core of the solid electrolyte particle a (M b )X c X' d The doping concentration of X' in the shell is less than that of the compound Li a (M b )X c X' d The doping concentration of X' in the core is Li a (M b )X c X' d The doping concentration of X' in the shell layer increases continuously. a (M b )X c X' d The doping concentration of X' in the graphite crystal shows a continuous increasing trend, and the slopes of the two increasing curves are consistent.

[0093] As shown in FIG9 , the compound Li in the core of the solid electrolyte particle a (M b )X c X' d The doping concentration of X' in the shell is less than that of the compound Li a (M b )X c X' d The doping concentration of X' in the core is Li a (M b )X c X' d The doping concentration of X' in the shell layer increases continuously. a (M b )X c X' d The doping concentration of X' in the core increases continuously, and the slope of the increasing curve of the core is smaller than that of the shell.

[0094] In other embodiments, the number of the shell layers is multiple, and the multiple shell layers are stacked in sequence in a direction away from the core portion, and in the direction away from the core portion, the compound Li in the multiple shell layers is a (M b )X c X' d The doping concentration of X' increases successively.

[0095] Through multi-shell setting, by regulating the Li compound in different shells a (Mb )X c X' d The doping concentration of X' in the solid electrolyte particles is different.

[0096] In some embodiments, the thickness of the shell layer is 10 nm to 1 μm, and the ratio of the thickness of the shell layer to the radius of the core portion is 1:(200-2).

[0097] The radius of the core is greater than the thickness of the shell, which is beneficial to ensuring high ionic conductivity in the core region and coverage of the SEI interface film in the shell region.

[0098] Another embodiment of the present invention provides a method for preparing the solid electrolyte particles as described above, wherein LiX, MX and a raw material containing X' are used as raw materials and the solid electrolyte particles are prepared by grinding or solvent co-dissolution recrystallization.

[0099] In the preparation method involving grinding and solvent co-dissolution recrystallization, the addition of different amounts of raw materials containing X' can be controlled during the preparation process to achieve control over the X' doping concentration in different regions of the solid electrolyte particles from the interior to the outer surface, thereby obtaining solid electrolyte particles with different X' doping concentration gradients. In the solid electrolyte particles prepared by this method, X' can in situ form an inorganic compound-rich SEI interface layer, improving the electrochemical stability and mechanical strength of the interface, reducing microcracks and core-shell separation during charge and discharge, and inhibiting the growth of lithium dendrites.

[0100] In some embodiments, the raw material containing X' is selected from lithium salts with X' as anion and Li as cation.

[0101] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0102] The raw materials LiX, MX and the raw material containing X' are fully charged and then ground to obtain the solid electrolyte particles shown in FIG1 .

[0103] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0104] The raw materials LiX and MX are mixed and then ground. During the grinding process, a raw material containing X' is added, and the feeding rate of the raw material containing X' is controlled to continuously decrease and / or gradually decrease, so that the compound Li is increased from the inside of the solid electrolyte particles to the outer surface of the solid electrolyte particles. a (M b )X c X' dThe doping concentration of X' shows a continuous decreasing and / or gradient decreasing trend, and the solid electrolyte particles shown in Figures 2 to 4 are obtained.

[0105] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0106] The raw materials LiX and MX are mixed and then ground. During the grinding process, a raw material containing X' is used for feeding. The feeding rate of the raw material containing X' is controlled to increase first and then decrease, so that the compound Li a (M b )X c X' d The doping concentration of X' in the middle increases first and then decreases, and the solid electrolyte particles shown in FIG5 are obtained.

[0107] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0108] The raw materials LiX and MX are mixed and then ground. During the grinding process, a raw material containing X' is used for feeding. The feeding rate of the raw material containing X' is controlled to first decrease and then increase, so that the compound Li a (M b )X c X' d The doping concentration of X' decreases first and then increases, and the solid electrolyte particles shown in FIG6 are obtained.

[0109] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0110] The raw materials LiX and MX are mixed and then ground. During the grinding process, a raw material containing X' is added, and the feeding rate of the raw material containing X' is controlled to increase continuously and / or gradually, so that the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a trend of continuous and / or gradient increase, and the solid electrolyte particles shown in Figures 7 to 9 are obtained.

[0111] In some embodiments, the grinding is ball milling, the ball-to-material ratio is 15:1 to 25:1, the ball milling time is 3 to 10 hours, and the ball milling speed is 400 to 600 rpm.

[0112] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0113] The raw materials LiX, MX and the raw material containing X' are all dissolved in an organic solvent, and then heated to evaporate the organic solvent to precipitate solid electrolyte particles, thereby obtaining the solid electrolyte particles shown in FIG1 .

[0114] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0115] The raw materials LiX and MX are dissolved in an organic solvent, and then heated to evaporate the organic solvent to precipitate solid electrolyte particles. During the evaporation of the organic solvent, the feeding rate of the raw material containing X' is controlled to decrease continuously and / or gradually, so that the compound Li a (M b )X c X' d The doping concentration of X' shows a trend of continuous decrease and / or gradient decrease and increase, and the solid electrolyte particles shown in Figures 2 to 4 are obtained.

[0116] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0117] The raw materials LiX and MX are dissolved in an organic solvent, and then heated to evaporate the organic solvent to precipitate solid electrolyte particles. During the evaporation of the organic solvent, the feeding rate of the raw material containing X' is controlled to increase first and then decrease, so that the compound Li a (M b )X c X' d The doping concentration of X' in the middle increases first and then decreases, and the solid electrolyte particles shown in FIG5 are obtained.

[0118] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0119] The raw materials LiX and MX are dissolved in an organic solvent, and then heated to evaporate the organic solvent to precipitate solid electrolyte particles. During the evaporation of the organic solvent, the feeding rate of the raw material containing X' is controlled to first decrease and then increase, so that the compound Li a (M b )X c X' d The doping concentration of X' decreases first and then increases, and the solid electrolyte particles shown in FIG6 are obtained.

[0120] In some embodiments, the method for preparing the solid electrolyte particles comprises the following steps:

[0121] The raw materials LiX and MX are dissolved in an organic solvent, and then heated to evaporate the organic solvent to precipitate solid electrolyte particles. During the evaporation of the organic solvent, the feeding rate of the raw material containing X' is controlled to increase continuously and / or gradually, so that the compound Li a (M b )X c X' d The doping concentration of X' in the middle shows a trend of continuous and / or gradient increase, and the solid electrolyte particles shown in Figures 7 to 9 are obtained.

[0122] Since X ions and X' ions in the organic solvent are in dynamic equilibrium, when the feeding rate of the raw material containing X' is controlled to increase continuously and / or gradually, the Li a (M b )X c X' d The doping concentration of X' in .

[0123] In some embodiments, the organic solvent includes one or more of hexane, heptane, octane, kerosene, toluene, p-xylene, ethylbenzene, carbon disulfide, carbon tetrachloride, chloropropane, bromohexane, chloroform and dichloromethane and isomers thereof.

[0124] In some embodiments, the organic solvent is selected from one or more of n-hexane, n-heptane, kerosene, p-xylene and carbon tetrachloride.

[0125] The organic solvent used has good solubility for the reaction raw materials, which promotes the reaction. a (M b )X c X' d When there is crystal water in the a (M b )X c X' d H2O will decompose to form impurities such as Li2O or MO, which will contaminate the product and lead to the degradation of the electrochemical performance of the solid electrolyte particles. As mentioned above, the polarity of the organic solvent is low, which can reduce the water content mixed in the organic solvent, thereby reducing the Li a (M b )X c X' d The probability of carrying crystal water.

[0126] In some embodiments, a hydrolysis inhibitor is added to the organic solvent, and the added mass of the hydrolysis inhibitor is 20% to 120% of the solid electrolyte particles. The hydrolysis inhibitor includes one or more of NH4Cl, I2, LiI or S.

[0127] By adding a hydrolysis inhibitor to the organic solvent, the Li a (M b )X c X' d Crystalline hydrate Li is produced during the crystallization process. a (M b )X c X' d H2O, improves the purity of solid electrolyte products.

[0128] In some embodiments, the precipitated solid electrolyte particles are filtered and dried, and the drying process includes one or more of vacuum heating, rotary evaporation drying, vacuum freeze drying, or microwave vacuum drying.

[0129] In some embodiments, when the drying treatment is a vacuum heating treatment, the temperature of the vacuum heating treatment is 40-120°C, the heating rate is 0.1-5°C / min, the cooling rate is 0.5-5°C / min, the time is 3-24h, and the vacuum degree is -0.1-0MPa g.

[0130] In a preferred embodiment, the vacuum heating treatment is performed at a temperature of 80 to 100° C. for a time of 6 to 12 hours.

[0131] In some embodiments, when the drying process is a rotary evaporation drying process, the temperature of the rotary evaporation drying process is 40 to 100° C., and the time is 4 to 16 hours.

[0132] In a preferred embodiment, the rotary evaporation drying process is carried out at a temperature of 80 to 100° C. and for a time of 6 to 12 hours.

[0133] In some embodiments, when the drying treatment is a vacuum freeze-drying treatment, the temperature of the vacuum freeze-drying treatment is -40 to -10°C, the time is 6 to 24 hours, and the vacuum degree is -0.1 to 0 MPa g.

[0134] In a preferred embodiment, the vacuum freeze-drying treatment is carried out at a temperature of -40 to -30°C and for a time of 6 to 12 hours.

[0135] In some embodiments, when the drying treatment is a microwave vacuum drying treatment, the power of the microwave vacuum drying treatment is 400 to 2000 W, the time is 3 to 24 hours, and the vacuum degree is -0.1 to 0 MPa g.

[0136] Another embodiment of the present invention provides a solid electrolyte comprising the solid electrolyte particles described above.

[0137] The solid electrolyte prepared by using the solid electrolyte particles as described above can form a protective SEI interface film on the contact interface with the negative electrode, inhibiting the progress of its interfacial reaction and playing a role in inhibiting the growth of lithium dendrites.

[0138] The present invention provides a semi-solid electrolyte comprising an electrolyte and the solid electrolyte particles described above.

[0139] In some embodiments, based on the total mass of the semi-solid electrolyte being 100%, the mass percentage of the electrolyte is 0.5 wt %-50 wt %, and the electrolyte includes a lithium salt, a solvent, and optional additives.

[0140] Specifically, the solvent may include carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), γ-butyrolactone (BL)), ethers (e.g., tetrahydrofuran (THF), 2-methyl-tetrahydrofuran (2-Me-THF), dimethoxydimethyl ether (DMM), 1,2-dimethoxyethane (DME), 1,3-dioxolane (DOL), nitriles (e.g., acetonitrile (AN)), etc.);

[0141] Lithium salts may include lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium hexafluoroarsenate (LiAsF6), other organic lithium salts (such as lithium trifluoromethanesulfonate (LiCF3SO), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoromethylsulfonyl-perfluorobutylsulfonylimide (LiTNFSI), lithium fluorosulfonyl-perfluorobutylsulfonylimide (LiFNFSI), lithium bis(oxalatoborate) (LiBOB), tris(trifluoromethylsulfonyl)methyllithium (LiC(SO2CF3)3), etc.).

[0142] Additives may include film-forming additives, conductive additives, flame retardant additives, overcharge protection additives, water and HF content control additives (i.e., additives that control the water and HF content in the electrolyte), low-temperature additives (i.e., general additives that improve low-temperature performance), and may also include negative electrode stabilizers, i.e., additives that improve the interface stability of the metallic lithium negative electrode (such as fluoroethylene carbonate (FEC), lithium nitrate (LiNO3), etc.).

[0143] Another embodiment of the present invention provides a positive electrode, comprising a positive electrode material layer, wherein the positive electrode material layer comprises a positive electrode active material and the solid electrolyte particles as described above.

[0144] By doping the positive electrode material layer with solid electrolyte particles, the ionic conductivity of the positive electrode material layer can be effectively improved, the internal resistance of the positive electrode material layer can be reduced, and the rate performance can be improved.

[0145] In some embodiments, based on the total mass of the positive electrode material layer being 100%, the mass percentage of the positive electrode active material is 50% to 99%, and the mass percentage of the solid electrolyte particles is 0.5% to 49.5%.

[0146] In some embodiments, the positive electrode active material includes lithium nickel cobalt manganese oxide (N x M y C z ,x+y+z=1)、Lithium manganese iron phosphate (LiFe x Mn y PO4, x+y=1), one or more of lithium iron phosphate, lithium manganate, lithium cobaltate, lithium nickelate, lithium-rich manganese-based, lithium nickel manganate (LMNO), and lithium vanadium phosphate (Li3V2(PO4)3, LiVOPO4).

[0147] In some embodiments, the positive electrode material layer further includes a positive electrode binder and a positive electrode conductor, and the positive electrode active material, the solid electrolyte particles, the positive electrode binder and the positive electrode conductor are blended to obtain the positive electrode material layer.

[0148] The positive electrode binder is selected from a polymer resin having adhesive properties, and the positive electrode conductor is selected from a carbon material.

[0149] Another embodiment of the present invention provides a battery comprising a positive electrode, an electrolyte and a negative electrode, wherein the positive electrode is selected from the positive electrode described above, and / or the electrolyte is selected from the solid electrolyte described above or the semi-solid electrolyte described above.

[0150] In some embodiments, the negative electrode is selected from lithium metal or lithium alloy.

[0151] In a preferred embodiment, the negative electrode is selected from at least one of lithium metal, lithium-indium alloy, lithium-magnesium alloy, lithium-arsenic alloy, lithium-tin alloy, lithium-silver alloy, and lithium-carbon alloy.

[0152] In some embodiments, the battery is an all-solid-state battery or a semi-solid-state battery.

[0153] Another embodiment of the present invention provides an electrical device including the battery described above.

[0154] The present invention is further described below with reference to the following examples.

[0155] Example 1

[0156] This embodiment is used to illustrate the preparation method of the solid-state battery disclosed in the present invention, which includes the following steps:

[0157] Preparation of solid electrolyte particles: The raw materials LiCl and InCl3 are mixed in a molar ratio of 3:1 and then ground. During the grinding process, LiF is added and the feeding rate of LiF is controlled to increase gradually so that the compound Li3InCl c F d The doping concentration of F in the core increases gradually, among which the Li3InCl c F d The molar ratio of F and Cl elements in the shell is 0.25:1, and the Li3InCl c F d The molar ratio of F and Cl elements is 2:1, the radius of the core is 250nm, and the thickness of the shell is 100nm.

[0158] Preparation of solid electrolyte: solid electrolyte particles are placed in a mold for tableting to obtain solid electrolyte.

[0159] Preparation of solid-state batteries: lithium cobalt oxide is used as the positive electrode and metallic lithium is used as the negative electrode. The positive electrode, negative electrode and solid electrolyte are assembled to form a solid-state battery.

[0160] Example 2

[0161] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0162] Li3InCl in the core c F d The molar ratio of F and Cl elements in the shell is 0.1:1, and the Li3InCl c F d The molar ratio of F and Cl elements is 1:1.

[0163] Example 3

[0164] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0165] Li3InCl in the core c F d The molar ratio of F and Cl elements in the shell is 0.2:1, and the Li3InCl c F dThe molar ratio of F and Cl elements is 1:1.

[0166] Example 4

[0167] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0168] Li3InCl in the core c F d The molar ratio of F and Cl elements in the shell is 0.1:1, and the Li3InCl c F d The molar ratio of F and Cl elements is 10:1.

[0169] Example 5

[0170] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0171] GaCl3 is used to replace InCl3 in Example 1, and Li3N is used to replace LiF in Example 1 to obtain Li3GaCl c N d .

[0172] Li3GaCl in the core c N d The molar ratio of N and Cl elements in the shell is 0.03:1, and the Li3GaCl c N d The molar ratio of N and Cl elements is 3:1.

[0173] Example 6

[0174] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0175] YCl3 is used to replace InCl3 in Example 1, and Li2S is used to replace LiF in Example 1 to obtain Li3YCl c S d .

[0176] Li3YCl in the core c S d The molar ratio of S and Cl elements in the shell is 0.05:1, and the Li3YCl c S d The molar ratio of S and Cl elements is 5:1.

[0177] Example 7

[0178] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0179] MgCl2 is used to replace InCl3 in Example 1, and LiI is used to replace LiF in Example 1 to obtain Li2MgCl c I d .

[0180] Li2MgCl in the core c I d The molar ratio of I and Cl elements in the shell is 0.01:1, and the Li2MgCl c I d The molar ratio of I and Cl elements is 10:1.

[0181] Example 8

[0182] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0183] Preparation of solid electrolyte particles: Raw materials LiCl, InCl3 and LiF were added in a molar ratio of 3:1:6 and then ground to obtain solid electrolyte particles as shown in Figure 1.

[0184] Example 9

[0185] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0186] Preparation of solid electrolyte particles: The raw materials LiCl and InCl3 are mixed in a molar ratio of 3:1 and then ground. During the grinding process, LiF is added and the feeding rate of LiF is controlled to decrease gradually so that the compound Li3InCl c F d The doping concentration of F in the core is gradually decreasing, among which the Li3InCl c F d The molar ratio of F and Cl elements in the shell is 10:1, and the Li3InCl c F d The molar ratio of F and Cl elements is 0.1:1, the radius of the core is 250nm, and the thickness of the shell is 100nm.

[0187] Comparative Example 1

[0188] This example is used to illustrate the method for preparing a solid-state battery disclosed in the present invention, and includes most of the steps in Example 1, except that:

[0189] Preparation of solid electrolyte particles: The raw materials LiCl and InCl3 are mixed in a molar ratio of 3:1 and then ground to obtain solid electrolyte particles.

[0190] Performance Testing

[0191] The solid-state battery prepared above was subjected to the following performance tests:

[0192] Cycle life test:

[0193] Use 0.3Cmin current to charge the battery cell to the upper cut-off voltage, the cut-off current is 0.05Cmin, and record the first cycle charging capacity Q 充1 , discharge at a current of 1Cmin until the battery voltage reaches the lower cut-off voltage, and record the discharge capacity Q 放1 The first cycle Coulomb efficiency is Q 放1 / Q 充1 Repeated cycle, battery cycle life is less than 80% discharge capacity·Q 放1 The number of cycles when .

[0194] The test results are entered in Table 1.

[0195] Table 1

[0196] From the test results in Table 1, it can be seen that the first-cycle Coulombic efficiency of Examples 1 to 7 (81% to 94%) is higher than that of Examples 8 and 9 (79%), and the first-cycle Coulombic efficiency of Examples 1 to 9 is better than that of the comparative example (72%); the cycle life of Examples 1 to 7 (200 to 300 cycles) is higher than that of Examples 8 and 9 (100 cycles), and the first-cycle Coulombic efficiency of Examples 1 to 9 is better than that of the comparative example (80 cycles).

[0197] Comparing the test results of the first cycle storage efficiency and cycle life, it can be seen that the solid electrolyte proposed in the present invention can significantly improve the cycle stability of the battery.

[0198] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A solid electrolyte particle, characterized in that, including a compound represented by the following general formula: Li a (M b )X c X’ d Wherein, M is a metal element, X is selected from Cl, and X' includes one or more of F ions, I ions, Br ions, N ions, P ions, S ions, CN - , oxoanions, pseudohalide anions; 0.5 < a < 5, 0.2 < b < 2, c + d*ε1 = a + b*ε2, where ε1 is the weighted average valence of X' and ε2 is the weighted average valence of the M element.

2. The solid electrolyte particles according to claim 1, characterized in that The M includes one or more of Ga, Y, In, Mg, Sr, Sc, Al, Fe, Zr, Hf, Ta, Nb, W, Mn, Zn, Yb, Co, Mo, Sn, Ca, Pb, Ti, Ru, and lanthanide metal elements.

3. The solid electrolyte particles according to claim 1, wherein The oxygen-containing anions include O 2- , CO3 2- , PO4 3- , P2O7 4- and SO4 2- and one or more of the following; the pseudohalide anions include SCN - , PF6 - , NH2 - , AlF4 - and BF4 - and one or more of the following.

4. The solid electrolyte particles according to claim 1, characterized in that, The molar ratio of X' to X elements in the overall solid electrolyte particles is (0.005 - 200):

1.

5. The solid electrolyte particles according to claim 1, characterized in that, In the direction from the inside to the outer surface of the solid electrolyte particles, the compound Li a (M b )X c X’ d has a uniform doping concentration of X'.

6. The solid electrolyte particles according to claim 1, wherein In the direction from the interior to the outer surface of the solid electrolyte particles, the doping concentration of X' in the compound Li a (M b )X c X’ d shows a continuous decreasing and / or gradient decreasing trend.

7. The solid electrolyte particles according to claim 1, characterized in that, From the inside of the solid electrolyte particles to the outer surface direction of the solid electrolyte particles, for the compound Li a (M b )X c X’, the doping concentration of X’ shows a trend of increasing first and then decreasing, or for the compound Li d (M a )X b )X c X’ d the doping concentration of X’ shows a trend of decreasing first and then increasing.

8. The solid electrolyte particles according to claim 1, wherein In the direction from the interior to the outer surface of the solid electrolyte particles, the doping concentration of X' in the compound Li a (M b )X c X’ d shows a continuous increasing and / or gradient increasing trend.

9. The solid electrolyte particles according to claim 8, wherein The solid electrolyte particles include a core and a shell layer, the shell layer is located outside the core, and the doping concentration of X' in the compound Li a (M b )X c X’ d in the shell layer is greater than the doping concentration of X' in the compound Li a (M b )X c X’ d in the core.

10. The solid electrolyte particles according to claim 9, characterized in that, The compound Li in the core part a (M b )X c X’ d In which, the molar ratio of X’ to X elements is (0.005 - 200):

1. The compound Li in the shell layer a (M b )X c X’ d In which, the molar ratio of X’ to X elements is (0.006 - 201):

1.

11. The solid electrolyte particles according to claim 9, characterized in that, In the direction from the core to the shell, the doping concentration of X' in the compound Li a (M b )X c X’ d in the shell shows a continuous increasing trend, and / or The compound Li in the shell a (M b )X c X' d has a consistent doping concentration of X', and / or The compound Li in the core part a (M b )X c X' d has a continuously increasing doping concentration of X', and / or The compound Li in the core part a (M b )X c X’ d has a consistent doping concentration of X'.

12. The solid electrolyte particles according to claim 9, characterized in that, The number of the shell layers is multiple, and the multiple shell layers are sequentially stacked in a direction away from the core part. In the direction away from the core part, the doping concentration of X' in the compound Li a (M b )X c X’ d in the multiple shell layers increases sequentially.

13. The solid electrolyte particles according to claim 9, characterized in that, The thickness of the shell layer is 10 nm to 1 μm, and the ratio of the thickness of the shell layer to the radius of the core is 1:(200 - 2).

14. The method for preparing the solid electrolyte particles according to any one of claims 1 to 13, characterized in that, Using LiX, MX, and a raw material containing X' as raw materials, the solid electrolyte particles are prepared by grinding or solvent co - dissolution and recrystallization.

15. The method for preparing the solid electrolyte particles according to claim 14, characterized in that, It includes the following operation steps: Mix the raw materials LiX and MX and grind them. During the grinding process, feed the raw material containing X' and control the feeding rate of the raw material containing X' to increase continuously and / or incrementally in gradients, so that in the direction from the inside to the outer surface of the solid electrolyte particles, the doping concentration of X' in the compound Li a (M b )X c X’ d shows a continuous increasing and / or gradient increasing trend.

16. The method for preparing the solid electrolyte particles according to claim 15, wherein, The grinding is ball milling, the ball - to - material ratio is 15:1 to 25:1, the ball - milling time is 3 to 10 h, and the ball - milling speed is 400 to 600 rpm.

17. The method for preparing the solid electrolyte particles according to claim 14, wherein It includes the following operation steps: Dissolve the raw materials LiX and MX in an organic solvent, and then heat to evaporate the organic solvent to precipitate solid electrolyte particles. During the evaporation of the organic solvent, control the feeding rate of the raw material containing X' to continuously increase and / or increase in a gradient manner, so that from the inside of the solid electrolyte particles to the outer surface direction of the solid electrolyte particles, the compound Li a (M b )X c X' d shows a continuous increasing and / or gradient increasing trend in the doping concentration of X'.

18. The method for preparing the solid electrolyte particles according to claim 17, wherein The organic solvent includes one or more of hexane, heptane, octane, kerosene, toluene, p - xylene, ethylbenzene, carbon disulfide, carbon tetrachloride, chloropropane, bromohexane, chloroform, and dichloromethane, and isomers of the above substances.

19. The method for preparing the solid electrolyte particles according to claim 17, wherein, A hydrolysis inhibitor is added to the organic solvent, and the added mass of the hydrolysis inhibitor is 20% - 120% of the solid electrolyte particles. The hydrolysis inhibitor includes one or more of NH4Cl, I2, LiI, or S.

20. The method for preparing the solid electrolyte particles according to claim 17, wherein The precipitated solid electrolyte particles are filtered and dried. The drying treatment includes one or more of vacuum heating treatment, rotary evaporation drying treatment, vacuum freeze - drying treatment, or microwave vacuum drying treatment.

21. A solid electrolyte, characterized in that, It includes the solid electrolyte particles as described in any one of claims 1 - 13.

22. A semi-solid electrolyte, characterized in that, It includes an electrolyte solution and the solid electrolyte particles as described in any one of claims 1 - 13.

23. A positive electrode, characterized in that, It includes a positive electrode material layer, and the positive electrode material layer includes a positive electrode active material and the solid electrolyte particles as described in any one of claims 1 - 13.

24. The positive electrode according to claim 23, characterized in that, Based on the total mass of the positive electrode material layer being 100%, the mass percentage of the positive electrode active material is 50% - 99%, and the mass percentage of the solid electrolyte particles is 0.5% - 49.5%.

25. A battery, characterized in that, It includes a positive electrode, an electrolyte, and a negative electrode. The positive electrode is selected from the positive electrodes as described in claim 23 or 24, and / or the electrolyte is selected from the solid electrolyte as described in claim 21 or the semi - solid electrolyte as described in claim 22.

26. An electrical device, characterized in that, It includes the battery as described in claim 25.

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