Ceramic soft composite for solid silicon anodes

Abstract

This invention relates to a ceramic soft composite for solid-state silicon anodes. An anode composite (AC) for the negative electrode of a solid-state lithium-ion battery comprises silicon active material particles, a carbon additive for conductivity, and a solid electrolyte combining a solid elastic electrolyte (SEE) with a solid inelastic electrolyte. The solid inelastic electrolyte is lithium thiophosphate or other ceramic lithium-ion conductor, and the SEE comprises lithium-doped ammonium or ion-closed borate. The SEE is uniformly diffused onto the combined particles by heating, wherein it is pressed to approximately 100% relative density under moderate pressure. The anode exhibits high stability during charge-discharge cycles of a solid-state lithium-ion battery prepared with this AC layer, demonstrating stable internal and external interfaces.

Description

Technical Field

[0001] This disclosure relates generally to electrochemical batteries, and more specifically to anodes for solid-state lithium batteries. Background Technology

[0002] Advanced solid-state rechargeable batteries consist of a solid electrolyte separator (SE-sep) sandwiched between an anode complex (AC) layer and a cathode complex (CathodeComp) layer. A typical AC layer comprises carbon, an active material, and a solid electrolyte material. The active material is a material with a high lithium storage capacity. The interface between these AC materials within the AC layer is called the intrinsic interface. The interface between the AC layer and the SE-sep layer is called the extrinsic interface. Among active materials, silicon is one of the most promising, possessing a high theoretical lithium storage capacity (approximately ten times that of graphite), high volumetric capacity, low lithiation potential, low discharge voltage, and moderate cost. Unfortunately, silicon tends to fracture during lithium insertion and extraction cycles, which is detrimental to both the intrinsic and extrinsic interfaces.

[0003] The intrinsic interfacial resistance of the AC layer increases due to mechanical cracking. Physical contact losses between the solid electrolyte, carbon, and / or anode active material (such as silicon) within the AC layer increase the resistance of the AC layer. The extrinsic interfacial resistance between the AC layers increases due to poor interfacial contact between the AC layer and the SE-sep layer. Mechanical separation during lithiation and delithiation at the interface between the SE-sep layer and the AC layer leads to capacity decay.

[0004] Therefore, the desired outcome is the realization of a more stable AC layer that overcomes the problems associated with interface degradation of silicon-containing anodes in solid-state lithium batteries. Summary of the Invention

[0005] In various non-limiting embodiments, an anode composite (AC) layer is disclosed, which is a silicone / carbon / solid electrolyte composite for forming a stable anode during repeated charge-discharge cycles of a solid-state Li battery. The solid electrolyte material of the AC comprises a soft elastic electrolyte (SEE) and a solid inelastic electrolyte. The SEE melts and diffuses around the particles and is uniformly distributed throughout the mixture of silicon particles (active material) and carbon particles (conductive additives) in the AC layer.

[0006] In various non-limiting embodiments, the solid electrolyte material comprises a solid inelastic electrolyte, which may be lithium thiophosphate (LPS) bonded to the SEE. The LPS may be selected from Li3PS4 or Li7P3S. 11 Li10 GeP2S 11 One or more of xLi₂S·yP₂S₅·(100-xy)LiX (X = Cl, Br, and I) or other solid lithium electrolytes, wherein x and y are values ​​of mass % and both x and y are in the range from about 33% to about 50%, wherein x+y is greater than about 75%. LPS can be prepared as a milled combination of Li₂S and P₂S₅ and / or GeS₂. SEE is an organic cation closed-borane anionic salt, wherein the organic cation has a flexible and / or asymmetric substituent attached to a positively charged nitrogen or phosphorus atom, and the closed-borane anion can be CB 11 H 12 - CB9H 10 - Or B 12 H 12 -2 , or its alternative variants.

[0007] In one embodiment provided herein, an organic cation closo-boron cluster salt is prepared in solution via a salt metathesis reaction between a metal cation (typically an alkali metal or alkaline earth metal cation) boron cluster salt and an organic cation salt (typically an organic cation salt containing a halide anion). The organic cation closo-boron cluster salt is doped with a Li salt, such as LiCB. 11 H 12 Or LiCB9H 10 Or both. Doping may include physically mixing two salts, heating to a temperature sufficient to at least partially melt the mixture, and further mixing as needed to form a doped SEE in solid form upon cooling to 25°C. In one embodiment provided herein, a method for preparing an AC layer includes a melt-diffusion process. The AC is formulated by grinding or milling about 20 to about 80 wt% silicon particles, about 5 to about 30 wt% carbon particles, and about 20 to about 50 wt% a solid electrolyte (wherein the solid electrolyte is LPS, SEE, or a combination thereof) to obtain a well-dispersed mixture, which is then heated to a temperature sufficient to melt the SEE but not exceeding the temperature at which LPS crystallizes. By molten impregnating the entire AC particle with the SEE, the relative density of the anode layer can be approximately 100% and the composition of the entire AC layer can be homogeneous when pressed under a relatively moderate pressure of less than two tons per square centimeter.

[0008] In one embodiment provided herein, the AC is included in an electrochemical device (such as a solid-state lithium battery) as an AC layer combined with a cathode layer and a solid electrolyte separator (SE-sep). The SE-sep can be used to transport Li during battery charging and discharging. + Any solid electrolyte. The cathode can have any structure used in solid-state lithium batteries.

[0009] These and other features of the solid silicon anode and its fabrication will become apparent from the following detailed description, which is exemplary and not limiting, when read in conjunction with the accompanying drawings and embodiments. Attached Figure Description

[0010] To better understand the processes and devices with solid silicon anodes, reference is made to the accompanying drawings regarding the specific variations and embodiments discussed herein, wherein:

[0011] Figure 1A-1D Scanning electron microscope (SEM) images of Si-LPS-SEE anode composite (AC) powder (1A) and granules (1B) pressed from it (which contain closed-borane anions in the SEE) are shown; and boron energy dispersive X-ray spectral (EDS) maps showing the uniform distribution of the SEE in the powder (1C) and granules (1D) after the SEE has melted and diffused uniformly throughout the Si-LPS powder are shown.

[0012] Figure 2 This is a bar graph showing the relative density of LPS and LPS-SEE pellets compressed under gradually increasing pressure, with LPS-SEE at approximately 1.5 tons / cm³. 2 Under pressure, it reaches approximately 100% of its maximum relative density, while LPS requires 5 tons / cm³. 2 The pressure is used to achieve its maximum LPS relative density, which is less than 100%.

[0013] Figures 3A-3C The diagram shows the construction of a half-cell by the following steps: (3A) pressing a lithium halide-doped lithium thiophosphate electrolyte; (3B) pressing the electrolyte with a Si-LPS-SEE anode composite or a Si-LPS anode composite according to one embodiment; and (3C) pressing the electrolyte-anode with a lithium-indium foil cathode.

[0014] Figures 4A-4B The diagram illustrates Si-LPS-SEE AC (4A) and Si-LPS AC (4B) according to one embodiment at 2.0 mA / cm² in their respective half-cells. 2SEM images after 100 cycles of the lower half-cell, with boxes located on some large cracks in the "hard" Si-LPS AC, while these cracks are clearly absent in the "soft" Si-LPS-SEE AC.

[0015] Figure 5 A composite plot of discharge capacity and coulombic efficiency retention of a half-cell having a “hard” Si-LPS AC and a “soft” Si-LPS-SEE anode composite according to one embodiment is shown, where the cycle at which the Si-LPS AC breaks is indicated by a dashed box.

[0016] Figure 6 The composite plots of the real and imaginary impedances of a “hard” Si-LPS AC and a “soft” Si-LPS-SEE AC according to one embodiment are shown before and after 100 cycles by electrochemical impedance spectroscopy (EIS), indicating that the resistance of the Si-LPS AC increases by approximately three times when it breaks.

[0017] Figures 7A-7C A diagram is shown of a symmetrical cell designed to determine the external resistance R3 between the AC layer and the SE-sep layer by means of the resistance difference between the internal resistances R4 and R2 of the SE-sep layer of the battery (7A), the AC layer of the battery (7B), and the symmetrical cell (7C).

[0018] Figure 8 The bar graphs show the external resistance between the AC layer and the SE-sep layer, respectively for the interface between the "hard" Si-LPS AC layer and the SE-sep layer, and for the interface between the "soft" Si-LPS-SEE AC layer and the SE-sep layer according to one embodiment.

[0019] It should be noted that, for the purpose of describing certain aspects, the accompanying drawings are intended to illustrate the general features of the methods, algorithms, and apparatus of the present technology. The drawings may not precisely reflect the features of any given aspect and are not necessarily intended to define or limit specific embodiments within the scope of the present technology. Detailed Implementation

[0020] This disclosure provides a composite for use as an anode in a lithium-ion battery. The anode composite (AC) is a layer comprising silicon powder containing carbon additives and a solid electrolyte combining a soft elastic electrolyte (SEE) and a solid inelastic electrolyte. The Si-C powder bound to the electrolyte is melt-diffused together with the SEE to form a homogeneous composite (homogeneous composition) providing a stable anode. This stable anode does not exhibit signs of fracture between the internal and external interfaces as observed in other anode composites without SEE. The ratio of Si to C and electrolyte can vary from about 20 to about 80 wt% silicon, from about 5 to about 30 wt% carbon, and from about 20 to about 50 wt% solid electrolyte.

[0021] This disclosure provides an anode electrolyte, which can be a combination of a solid inelastic electrolyte (such as lithium thiophosphate (LPS)) and a SEE, wherein the SEE can be an organic cation closed-borate anion salt, which may be doped with lithium closed-borate. The combination of LPS and SEE is such that the SEE constitutes from about 1 to about 50 mol% of the anode electrolyte. The LPS can be Li3PS4, Li7P3S, etc. 11 Li 10 GeP2S 11 Alternatively, it can be xLi₂S·yP₂S₅·(100-xy)LiX (X = Cl, Br, and I), where x and y are mass % values, both ranging from about 33% to about 50%, with x+y greater than about 75%. LPS can be prepared by ball milling or other grinding methods using combinations of Li₂S and P₂S₅ and / or GeS₂. Alternatively, LPS can be formed using solution methods or microwave-assisted methods. Solid-state inelastic electrolytes may not be LPS, such as NASICON-type Li-ion electrolytes, such as Li₂S·yP₂S₅·(100-xy)LiX (X = Cl, Br, and I), where x and y are mass % values, both ranging from about 33% to about 50%, with x+y greater than about 75%. 1.3 Al 0.3 Ti 1.7 (PO4)3(LATP), Li 1+x+y Al x Ti 2-x Si γ P 3-γ O 12 LiNi 0.6 Co 0.2 Mn 0.2 O2, Li 0.33 La 0.55 TiO3(LLTO), Li 9.54 Si 1.74 P 1.44 Si 11.7 Cl 0.3And these and their complexes with other fillers (such as Li6ZnNb4O) 14 (LZNO) and LPS). SEE can be an organic cation closed-borane anionic salt, wherein the organic cation has a flexible and / or asymmetric substituent attached to a positively charged nitrogen or phosphorus atom, and the closed-borane anion can be CB. 11 H 12 - CB9H 10 - B 12 H 12 -2 , its alternative variants, and their combinations.

[0022] This disclosure provides a method for forming organic cation closed-boron cluster salts through salt metathesis between a metal cation (typically an alkali metal or alkaline earth metal cation) boron cluster salt and an organic cation salt (typically having a halide anion) in solution. The organic cation closed-boron cluster salts are doped with Li salts, such as LiCB. 11 H 12 Or LiCB9H 10 Or both. Doping may involve physically mixing two salts, heating to a temperature sufficient to at least partially melt the mixture, and further mixing as needed to form a doped SEE as a solid upon cooling to 25°C. The SEE has an organic cation with the structure [(CR 1 R 2 ) n ] w Z(R 3 ) 4-2w + ammonium ions or Ions, where: n is 4 to 6; w is 0 to 2; Z is N or P; R 3 The group is independently a C1-C8 alkyl or C6-C group that is either unsubstituted or substituted once or multiple times with fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy, or monofluorinated to perfluorinated phenoxy. 10 Aryl group, wherein any alkyl or alkoxy group is straight-chain, branched, or cyclic; R 1 and R 2 The functional groups are independently hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C6-C 10 Aryl or C6-C 10 Aryloxy group, wherein the carbon atom is not substituted or is substituted once or multiple times by fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy, or monofluorinated to perfluorinated phenoxy, and wherein any alkyl or alkoxy group is straight-chain, branched, or cyclic. When w is 0 or 1, R3 The group may include at least two different structures, or when all R groups are present. 3 When the groups are the same, R 3 The group contains a chiral center but the combination of R 3 It is racemic. When w is 2, the two spiroammonium compounds or ions of [(CR 1 R 2 ) n Z + The ring structures can be different, or when two [(CR 1 R 2 ) n Z + When the rings are the same, at least one CR 1 R 2 Having different R 1 and R 2 Group, and the R 1 and R 2 The groups are randomly located on two faces of the structure, for example, randomly located along the axial and equatorial positions of an n=5 ring. The Z atom can be, but must not be, a chiral center, or R... 1 R 2 Or R 3 Any of the groups can be, but does not have to be, chiral. A variety of different organic cations can combine with one or more closed-borate anions to form an organic cation closed-borate anionic salt. Additional Li closed-borates can have ammonium or... Closed-borates are the same as or different from closed-borates.

[0023] This disclosure provides information containing organic cations or Li + The closed-type borate anion can be B 12 H 12 -2 CB 11 H 12 -1 CB9H 10 -1 Or one or more of its substituted derivatives. The substituted derived closed-borate anion may have a structural C y B a-y H a-z X z -(2-y) , where: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z is 0 to a; X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl can be straight-chain, branched or cyclic, and wherein any substituent can be partially or completely halogenated.

[0024] Among the various embodiments provided herein, a method for forming carbon-doped silicon powder (AC) is proposed, which can be achieved by grinding or milling silicon metal with graphite, carbon black, fullerene, nanotubes, nanopowders, nanofibers, or any form of carbon capable of enhancing the conductivity of the powder. Milling can be of any form, including ball milling and air jet milling. Milling is performed until the Si-C particle size is less than about 10 μm, for example, less than about 1 μm, 300 nm, or less than about 50 nm. The crystallite size of the particles can be less than about 1 μm, 300 nm, less than 100 nm, or less than about 50 nm.

[0025] LPS and soft organic ammonium or A cationic closed-cell borate anionic salt anode electrolyte (where LPS is from about 50 to about 99 mol% and SEE is doped with closed-cell borate) is milled or rolled to a size of less than about 10 μm, 1 μm, for example, less than about 300 nm, or less than about 50 nm. The anode electrolyte can then be mixed with Si-C and AC formed from powders combined by milling or rolling, followed by heating to melt the SEE electrolyte and form a dense AC layer. The inclusion of a “soft” SEE electrolyte allows for the production of a dense AC layer for Li batteries by pressing at a pressure significantly lower than that required to form a dense AC layer without a “soft” SEE electrolyte. For example, in the case of SEE, less than 2 t / cm². 2 The molding pressure can be greater than about 5 tons / cm compared to when there is no SEE. 2 The "hard" AC layer formed under pressure is a denser AC layer with a relative density comparable to about 100% of the relative density of a theoretically fully dense material.

[0026] The following embodiments further illustrate various aspects of this disclosure. It should be understood that these embodiments are provided to illustrate specific implementations of this disclosure and should not be construed as limiting the scope of this disclosure in any particular respect or restricting its scope to any particular aspect.

[0027] Example 1

[0028] Li3PS4(LPS) was formed by ball milling Li2S and P2S5 in a molar ratio of 3:1 at 25°C for 50 hours under argon atmosphere.

[0029] Example 2

[0030] Synthesis of SEE: SEE is prepared by metathesis as follows: LiCB is prepared by grinding LiCB under argon atmosphere using a mortar and pestle. 11 H 12 (3.85g) and LiCB9H10 (3.24g) and 1-butyl-1-methylpyrrolidine chloride (Pyr 14 Grind (Cl)(3.31g) together for 30 minutes to obtain a uniform powder. Transfer the uniform powder to a mixing container and keep stirring at 160°C for 24 hours.

[0031] Example 3

[0032] Comparative anodic composite (AC) Si-LPS: The Si:LPS:carbon combination with a mass ratio of 55:35:10 was ground for 15 minutes at 25°C under argon atmosphere using a mortar and pestle.

[0033] Example 4

[0034] Anodic composite (AC) Si-LPS-SEE: LPS and SEE were combined and ground in a mortar with a pestle for 15 minutes at 25°C under argon atmosphere. Silicon and carbon were added to the mortar, and grinding was continued at 25°C under argon atmosphere for another 15 minutes. The combined, ground AC powder was heated to 120°C and held for 30 minutes to uniformly diffuse the SEE into the bulk, and then cooled to room temperature to prepare AC.

[0035] AC powder shows Figure 1A The morphology shown remains essentially compacted when compressed into 1.128 cm diameter particles under pressure of 10 tons. Figure 1B As shown. Powder and granules were analyzed by EDS spectroscopy, as shown below. Figure 1C and 1D As shown, boron is uniformly distributed throughout the AC and AC layers.

[0036] Example 5

[0037] Relative density of LPS-SEE composite: LPS-SEE composite pellets were pressed under various pressures to determine the density variation of the anode material pellets and to define the minimum feasible molding pressure for obtaining high-density pellets that are sufficiently flexible to accommodate volume expansion and contraction during charge-discharge cycles. Pellet dimensions were measured to calculate the relative density of LPS and LPS-SEE composite obtained under increased molding pressures. Figure 2 The diagram shows the relative density difference between LPS and the LPS-SEE composite, as well as the change in relative density with applied pressure. Compared to SEE-free pellets, the LPS-SEE composite achieves a higher, almost constant, maximum relative density at lower applied pressure. This indicates that LPS-SEE is a softer composite. The softer composite mitigates the mechanical stress imposed during silicon expansion and contraction during lithiation and delithiation.

[0038] Example 6

[0039] Anode composite half-cell: such as Figures 3A-3C The drawing illustrates that solid-state batteries are fabricated by: (3A) pressing solid electrolyte powder into granules, (3B) dispersing cathode material on the surface of the solid electrolyte and pressing it into a stack, and (3C) dispersing anode material on the opposite side of the solid electrolyte and pressing it into a stack for the third time. In this manner, an anode composite / solid electrolyte / lithium-indium battery is fabricated, wherein: (3A) 80 to 300 mg of lithium halide-doped lithium thiophosphate is cold-pressed into granules with a diameter of 1.128 cm using a pressure of 0.5 to 10 tons; (3B) 1 to 300 mg of Si-LPS or Si-LPS-SEE powder is dispersed on the solid electrolyte granules and pressed into a stack using a pressure of 0.1 to 6 tons; and (3C) lithium-indium foil is placed on the opposite side of the solid electrolyte and pressed into a stack under a pressure of 0 to 4 tons.

[0040] Example 7

[0041] Stability of the anode composite: The “softness” provided by Si-LPS-SEE AC allows for robustness that cannot be obtained by Si-LPS AC without OIPC content. Figure 4A SEM analysis of Si-LPS AC pellets showed cracking during cycling, which differed from that observed after cycling. Figure 4B The Si-LPS-SEE AC granules form a striking contrast. Through the anodic composite, such as... Figure 5 The changes in capacitance retention and coulombic efficiency during the cycle are shown, as well as... Figure 6 The conduction electrochemical impedance spectroscopy shown is used to confirm the cycling stability, which demonstrates the superior stability of the “soft” Si-LPS-SEE AC and the early cracking of the “hard” Si-LPS AC after about 25 cycles, with its limiting resistance increasing by about three times after fracture.

[0042] Example 8

[0043] Li-Li symmetric cell: A symmetric cell with a pair of lithium electrodes constructed to have Figures 7A-7C The structure shown is used to examine the resistance of the external interface between the AC layer and the contact separator - SE layer. To isolate the resistance caused by the external interface, batteries A, B, and C are constructed as follows... Figures 7A-7C As shown, the total internal resistance generated by the SE-sep layer and AC layer is subtracted from the two external resistances from the two interfaces between the SE-sep layer and AC layer. The external interface resistance R3 is equal to the resistance measured in battery C minus the resistances of batteries A and B divided by 2.

[0044] R3 = (Battery 7C - Battery 7B - Battery 7A) / 2.

[0045] like Figure 8 As shown, the external resistance between the obtained SE-sep layer and the “soft” Si-LPS-SEE AC layer is much smaller than that between the SE-sep layer and the “hard” Si-LPS AC layer, by about one-third.

[0046] The foregoing description is illustrative in nature and is not intended to limit this disclosure, its application, or its uses. As used herein, at least one of the phrases A, B, and C should be interpreted as representing logic (A or B or C) using the non-exclusive logic "OR". It should be understood that the various steps within the method may be performed in different orders without altering the principles of this disclosure. Scope of disclosure includes the full scope and subscopes within the entire scope.

[0047] The headings (such as “Background Art” and “Abstract”) and subheadings used herein are for general organization of the subject matter within this disclosure and are not intended to limit the disclosure of this technology or any aspect thereof. The description of multiple embodiments having the described features is not intended to exclude other embodiments having additional features, or other embodiments combining different combinations of the described features.

[0048] As used herein, the terms “comprising” and “including” and variations thereof are intended to be non-limiting, such that a description of consecutive items or a list does not exclude the possibility of other similar items that may be used in the devices and methods of the present technology. Similarly, the terms “may,” “can,” and “may,” and variations thereof are intended to be non-limiting, such that a description of an embodiment that may or can include certain elements or features does not exclude other embodiments of the present technology that do not contain those elements or features.

[0049] The extensive teachings of this disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes specific embodiments, its true scope should not be limited as other modifications will become apparent to those skilled in the art upon review of the specification and appended claims. Reference to an aspect or aspect herein means that a particular feature, structure, or characteristic described in connection with an embodiment or particular system is included in at least one embodiment or aspect. The appearance of the phrase “aspect” (or variations thereof) does not necessarily refer to the same aspect or embodiment. It should also be understood that the various method steps discussed herein need not be performed in the same order as depicted, and not every method step is required in every aspect or embodiment.

[0050] The foregoing description of the embodiments has been provided for illustrative and descriptive purposes. It is not intended to be exhaustive or limiting of this disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but are interchangeable where applicable and can be used in selected embodiments, even if not specifically shown or described. Variations are also possible in various ways. Such variations should not be considered a departure from this disclosure, and all such modifications are intended to be included within the scope of this disclosure.

[0051] While specific embodiments have been described, alternatives, modifications, variations, improvements, and substantial equivalents will come to mind by the applicant or others skilled in the art that are currently unforeseeable or may not be foreseeable at present. Therefore, the appended claims, both submitted and amended, are intended to cover all such alternatives, modifications, variations, improvements, and substantial equivalents.

Claims

1. An anode composite for lithium storage and release, comprising: Multiple silicon particles; Multiple carbon particles; and Multiple solid electrolyte particles, in, The solid electrolyte particles include solid elastic electrolytes and solid inelastic electrolytes. The solid elastic electrolyte comprises: At least one of the following structures of ammonium ions or ion: [(CR 1 R 2 ) n ] w Z(R 3 ) 4-2w + , Where: n is 4 to 6; w is 0 to 2; Z is N or P; R 3 The groups are independently C1-C8 alkyl or C6-C 10 Aryl group, wherein it is not substituted or is substituted once or more by fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy or monofluorinated to perfluorinated phenoxy, and wherein any alkyl or alkoxy group is straight-chain, branched or cyclic. R 1 and R 2 The functional groups are independently hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C6-C 10 Aryl or C6-C 10 An aryloxy group, wherein it is unsubstituted or substituted once or multiple times with fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy, or monofluorinated to perfluorinated phenoxy, wherein any alkyl or alkoxy group is straight-chain, branched, or cyclic; and At least one selected from CB 11 H 12 - CB9H 10 - B 12 H 12 -2 and C y B a-y H a-z X z -(2-y) Closed-type borane anion, Where: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z ranges from 0 to a; and X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl group may be straight-chain, branched or cyclic, and wherein any substituent may be partially or completely halogenated, or any combination thereof; The solid inelastic electrolyte contains lithium ions, and the solid inelastic electrolyte contains at least one of the following: Li3PS4; Li7P3S 11 Li 10 GeP2S 11 ;xLi₂S·yP₂S₅·(100-xy)LiX, where X is Cl, Br, or I, x and y are from 33% to 50% by mass, and x+y is greater than 75%; a combination of grinding or milling Li₂S with P₂S₅ and / or GeS₂; Li 1.3 Al 0.3 Ti 1.7 (PO4)3(LATP); Li 0.33 La 0.55 TiO3(LLTO); Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ; any combination thereof; and with Li6ZnNb4O 14 (LZNO) composite arbitrary solid inelastic electrolyte; The silicon particles, the carbon particles, and the solid electrolyte particles are uniformly dispersed; and the solid elastic electrolyte is diffused throughout the anode composite.

2. The anode composite for lithium storage and release according to claim 1, wherein, The anode composite comprises from 20% to 80% by weight of the silicon particles, from 5% to 30% by weight of the carbon particles, and from 20% to 50% by weight of the solid electrolyte particles.

3. The anode composite for lithium storage and release according to claim 1, wherein, The silicon particles have a cross-sectional size ranging from 50 nm to 10,000 nm, the carbon particles have a cross-sectional size ranging from 50 nm to 10,000 nm, and the solid electrolyte particles have a cross-sectional size ranging from 50 nm to 10,000 nm.

4. The anode composite for lithium storage and release according to claim 1, wherein, The anode compound has a strength greater than 1.5 tons / cm³. 2 It has a relative density of 100% when pressed under pressure.

5. The anode composite for lithium storage and release according to claim 1, wherein, The ammonium ion or The ion has the following structure: Z(R 3 )4 + and at least one of the other R 3 Different structures of R 3 , or R 3 Contains chiral centers and multiple R 3 The group is racemic; [(CR 1 R 2 ) n Z(R) 3 )2 + and at least one of the other R 3 Different structures of R 3 , or R 3 Contains chiral centers and multiple R 3 The group is racemic, and / or [(CR 1 R 2 ) n Z + The ring has at least one CR 1 R 2 The CR 1 R 2 Having different from R 2 R 1 ; or Having a structure [(CR 1 R 2 ) n ]2Z + Spiroammonium or Ions, of which two [(CR 1 R 2 ) n Z + The rings are different, or [(CR 1 R 2 ) n Z + The rings are identical and have at least one different R 1 and R 2 CR of groups 1 R 2 And R 1 and R 2 The groups are randomly located on two faces of the structure.

6. The anode composite for lithium storage and release according to claim 1, wherein, The solid-state elastic electrolyte further comprises at least one lithium salt having a closed-borane anion, wherein the closed-borane anion is selected from CB. 11 H 12 - CB9H 10 - B 12 H 12 -2 and C y B a-y H a-z X z -(2-y) One or more of the following, wherein: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z ranges from 0 to a; and X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl group may be straight-chain, branched or cyclic, and wherein any substituent may be partially or completely halogenated, or any combination thereof.

7. A lithium-ion battery, comprising: Anode compound, comprising: Silicon particles ranging from 20% to 80% by weight; Carbon particles ranging from 5% to 30% by weight; and Solid electrolyte particles ranging from 20% to 50% by weight, in, The solid electrolyte particles include solid elastic electrolytes and solid inelastic electrolytes. The solid elastic electrolyte comprises: At least one of the following structures of ammonium ions or ion: [(CR 1 R 2 ) n ] w Z(R 3 ) 4-2w + , Where: n is 4 to 6; w is 0 to 2; Z is N or P; R 3 The groups are independently C1-C8 alkyl or C6-C 10 Aryl group, wherein it is not substituted or is substituted once or more by fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy or monofluorinated to perfluorinated phenoxy, and wherein any alkyl or alkoxy group is straight-chain, branched or cyclic. R 1 and R 2 The functional groups are independently hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C6-C 10 Aryl or C6-C 10 An aryloxy group, wherein it is unsubstituted or substituted once or multiple times with fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy, or monofluorinated to perfluorinated phenoxy, wherein any alkyl or alkoxy group is straight-chain, branched, or cyclic; and At least one selected from CB 11 H 12 - CB9H 10 - B 12 H 12 -2 and C y B a-y H a-z X z -(2-y) The closed-form borane anion, wherein: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z is from 0 to a; and X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl group may be straight-chain, branched or cyclic, and wherein any substituent may be partially or completely halogenated, or any combination thereof; The solid inelastic electrolyte contains lithium ions, and the solid inelastic electrolyte contains at least one of the following: Li3PS4; Li7P3S 11 Li 10 GeP2S 11 ;xLi₂S·yP₂S₅·(100-xy)LiX, where X is Cl, Br, or I, x and y are from 33% to 50% by mass, and x+y is greater than 75%; a combination of grinding or milling Li₂S with P₂S₅ and / or GeS₂; Li 1.3 Al 0.3 Ti 1.7 (PO4)3(LATP); Li 0.33 La 0.55 TiO3(LLTO); Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ; any combination thereof; and with Li6ZnNb4O 14 (LZNO) composite arbitrary solid inelastic electrolyte; The silicon particles, the carbon particles, and the solid electrolyte particles are uniformly dispersed in the anode composite, and the solid elastic electrolyte is distributed throughout the anode composite.

8. The lithium battery according to claim 7, wherein, The solid-state elastic electrolyte further comprises at least one lithium salt having a closed-borane anion, wherein the closed-borane anion is selected from CB. 11 H 12 - CB9H 10 - B 12 H 12 -2 and C y B a-y H a-z X z -(2-y) One or more of the following, wherein: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z ranges from 0 to a; and X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl group may be straight-chain, branched or cyclic, and wherein any substituent may be partially or completely halogenated, or any combination thereof.

9. A method for preparing an anode, the method comprising: Multiple silicon particles, multiple carbon particles, and multiple solid electrolyte particles are combined to form a combined powder, wherein the solid electrolyte particles include solid elastic electrolytes and solid inelastic electrolytes. Grinding or milling the powder of the combination to form an anodic compound powder; The anode composite powder is heated to a temperature higher than the melting temperature of the solid elastic electrolyte but lower than the crystallization temperature of the solid inelastic electrolyte; and The anode is formed by pressing the anode compound powder into an anode compound layer with a relative density of 100%. The solid elastic electrolyte comprises: At least one of the following structures of ammonium ions or ion: [(CR 1 R 2 ) n ] w Z(R 3 ) 4-2w + , Where: n is 4 to 6; w is 0 to 2; Z is N or P; R 3 The groups are independently C1-C8 alkyl or C6-C 10 Aryl group, wherein it is not substituted or is substituted once or more by fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy or monofluorinated to perfluorinated phenoxy, and wherein any alkyl or alkoxy group is straight-chain, branched or cyclic. R 1 and R 2 The functional groups are independently hydrogen, C1-C8 alkyl, C1-C8 alkoxy, C6-C 10 Aryl or C6-C 10 An aryloxy group, wherein it is unsubstituted or substituted once or multiple times with fluorine, alkyl, monofluorinated to perfluorinated alkyl, alkoxy, monofluorinated to perfluorinated alkoxy, phenyl, monofluorinated to perfluorinated phenyl, phenoxy, or monofluorinated to perfluorinated phenoxy, wherein any alkyl or alkoxy group is straight-chain, branched, or cyclic; and At least one selected from CB 11 H 12 - CB9H 10 - B 12 H 12 -2 and C y B a-y H a-z X z -(2-y) The closed-form borane anion, wherein: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z is from 0 to a; and X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl group may be straight-chain, branched or cyclic, and wherein any substituent may be partially or completely halogenated, or any combination thereof; The solid inelastic electrolyte comprises at least one of the following: Li3PS4; Li7P3S 11 Li 10 GeP2S 11 ;xLi₂S·yP₂S₅·(100-xy)LiX, where X is Cl, Br, or I, x and y are from 33% to 50% by mass, and x+y is greater than 75%; a combination of grinding or milling Li₂S with P₂S₅ and / or GeS₂; Li 1.3 Al 0.3 Ti 1.7 (PO4)3(LATP); Li 0.33 La 0.55 TiO3(LLTO); Li 9.54 Si 1.74 P 1.44 S 11.7 Cl 0.3 ; any combination thereof; and with Li6ZnNb4O 14 (LZNO) composite arbitrary solid inelastic electrolyte.

10. The method for preparing an anode according to claim 9, wherein the silicon particles, the carbon particles, and the solid electrolyte particles have a cross-sectional size from 50 nm to 1000 nm.

11. The method for preparing an anode according to claim 9, wherein, The solid-state elastic electrolyte further comprises at least one lithium salt having a closed-borane anion, wherein the closed-borane anion is selected from CB. 11 H 12 - CB9H 10 - B 12 H 12 -2 and C y B a-y H a-z X z -(2-y) One or more of the following, wherein: y is 0 or 1; when y is 0, a is 12, and when y is 1, a is 10 or 12; z ranges from 0 to a; and X is independently a halogen, alkyl, alkoxy, aryl, alkylaryl, aralkyl and / or aryloxy substituent, wherein the alkyl group may be straight-chain, branched or cyclic, and wherein any substituent may be partially or completely halogenated, or any combination thereof.

12. The method for preparing an anode according to claim 9, wherein the combining step comprises: The plurality of silicon particles are mixed with the plurality of carbon particles to form a silicon-carbon mixture, and the silicon-carbon mixture is ground or milled to form a mixture of silicon particles and carbon particles; The solid elastic electrolyte is mixed with the solid inelastic electrolyte to form a plurality of solid electrolyte particles; and The mixture of silicon particles and carbon particles is mixed with the plurality of solid electrolyte particles to form the combined powder.

13. The method for preparing an anode according to claim 9, wherein the grinding or milling step includes ball milling, air jet milling, or grinding with a pestle in a mortar.

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