SILICON-BASED NEGATIVE ELECTRODE MATERIAL CONTAINING SILICATE SKELETON, NEGATIVE ELECTRODE PLATE, AND LITHIUM BATTERY

Abstract

A silicon-based negative electrode material containing a silicate skeleton, a negative electrode plate and a lithium battery. The silicon-based negative electrode material comprises a modified silicon monoxide material having a dispersedly distributed silicate material inside same. The general formula of the modified silicon monoxide material is MxSiOy, with 1<x<6, 3<y<6, element M comprising one or more of Mg, Ni, Cu, Zn, Al, Na, Ca, K, Li, Fe and Co, and the grain size being 0.5-100 nm. In the modified silicon monoxide material, the content of the silicate material is 5-60% of the total mass of the modified silicon monoxide material. The dispersedly distributed silicate material forms a skeleton structure of the silicon-based negative electrode material, does not undergo a physicochemical reaction along with the lithium removal and lithium intercalation of the silicon-based negative electrode material in the cycle process, and maintains the original structure thereof after multiple cycles.

Claims

1. A Silicon-based negative electrode material containing a silicate skeleton, wherein the Silicon-based negative electrode material comprises a modified SiO.sub.x material with a silicate material dispersed inside; a general formula of the modified SiO.sub.x material with a silicate material dispersed inside is M.sub.xSiO.sub.y, 1 ≤ x < 6, 3 ≤ y < 6, wherein element M is one or more of Mg, Ni, Cu, Zn, Al, Na, Ca, K, Li, Fe and Co, a grain size of the modified SiO.sub.x material is 0.5-100 nm, and the silicate material accounts for 5-60% of a total mass of the modified SiO.sub.x material; and the silicate material dispersed inside the modified SiO.sub.x constitutes a skeleton structure of the Silicon-based negative electrode material, does not have physical and chemical reactions with lithium intercalation and deintercalation of the Silicon-based negative electrode material during a cycling process, and keeps an original structure even after multiple cycles.

2. The Silicon-based negative electrode material of claim 1, wherein the Silicon-based negative electrode material further comprises a carbon coating layer, and the modified SiO.sub.x material is coated with the carbon coating layer with a thickness of 1-100 nm.

3. The Silicon-based negative electrode material of claim 1, wherein the grain size of the modified SiO.sub.x material is 2-30 nm, and the silicate material accounts for 10-30% of the total mass of the modified SiO.sub.x material.

4. The Silicon-based negative electrode material of claim 1, wherein an average particle diameter (D.sub.50) of the Silicon-based negative electrode material is 0.1-40 .Math.m, and a specific surface area of the Silicon-based negative electrode material is 0.5-40 m.sup.2/g.

5. The Silicon-based negative electrode material of claim 4, wherein the average particle diameter (D.sub.50) of the Silicon-based negative electrode material is 2-15 .Math.m, and the specific surface area is 1-10 m.sup.2/g.

6. The Silicon-based negative electrode material of claim 1, wherein when the element M is Mg, a corresponding Mgsilicate material is MgSiO.sub.3 and/or Mg.sub.2SiO.sub.4, maximum X-ray diffraction (XRD) peaks of MgSiO.sub.3 are located at one or more of 28.1 degrees, 31.1 degrees, 34.8 degrees, 34.9 degrees and 36.9 degrees, and a maximum XRD peak of Mg.sub.2SiO.sub.4 is located at 36.5 degrees; when the element M is Ni, a corresponding Ni silicate is NiSiO.sub.4, and a maximum XRD peak of NiSiO.sub.4 is located at 37.0 degrees; when the element M is Cu, a corresponding Cu silicate is CuSiO.sub.3 and a maximum XRD peak of CuSiO.sub.3 is located at 12.2 degrees; when the element M is Zn, a corresponding Zn silicate is ZnSiO.sub.3 and/or Zn.sub.2SiO.sub.4, maximum XRD peaks of ZnSiO.sub.3 are located at 31.0 degrees and/or 34.0 degrees, and maximum XRD peaks of Zn.sub.2SiO.sub.4 are located at one of more of (31.0 degrees and 34.0 degrees), 31.5 degrees, 31.7 degrees, 33.1 degrees, 36.5 degrees and 37.0 degrees; when the element M is Al, a corresponding Al silicate is Al.sub.2SiO.sub.5, and a maximum XRD peak of Al.sub.2SiO.sub.5 is located at 26.1 degrees and/or 28.0 degrees; when the element M is Na, a corresponding Nasilicate is Na.sub.2SiO.sub.3 and/or Na.sub.4SiO.sub.4, a maximum XRD peak of Na.sub.2SiO.sub.3 is located at 29.4 degrees, and maximum XRD peaks of Na.sub.4SiO.sub.4 are located at 13.0 degrees and 23.2 degrees; when the element M is Ca, a corresponding Ca silicate is CaSiO.sub.3 and/or Ca.sub.2SiO.sub.4, maximum XRD peaks of CaSiO.sub.3 are located at 25.3 degrees and/or 30.0 degrees, and maximum XRD peaks of Ca.sub.2SiO.sub.4 are located at one of more of 32.0 degrees, 32.1 degrees, 32.5 degrees, 32.7 degrees, 32.8 degrees, 33.0 degrees and 33.2 degrees; when the element M is K, a corresponding K silicate is K.sub.4SiO.sub.4, and maximum XRD peaks of K.sub.4SiO.sub.4 are located at 30.4 degrees and 37.8 degrees; when the element M is Li, a corresponding Li silicate is Li.sub.2SiO.sub.3 and/or Li.sub.4SiO.sub.4, maximum XRD peaks of Li.sub.2SiO.sub.3 are located at 18.9 degrees and/or 27.0 degrees, and maximum XRD peaks of Li.sub.4SiO.sub.4 are located at (22.2 degrees and 33.8 degrees) and/or 34.9 degrees; when the element M is Fe, a corresponding Fe silicate is FeSiO.sub.3 and/or Fe.sub.2SiO.sub.4, a maximum XRD peak of FeSiO.sub.3 is located at 32.7 degrees, and a maximum XRD peak of Fe.sub.2SiO.sub.4 is located at 63.8 degrees; and when the element M is Co, a corresponding Co silicate is Co.sub.2SiO.sub.4, and maximum XRD peaks of Co.sub.2SiO.sub.4 are located at 36.4 degrees, 36.5 degrees and 36.6 degrees.

7. A negative electrode plate, wherein the negative electrode plate comprises the Silicon-based negative electrode material containing the skeleton structure of claim 1.

8. A lithium battery, wherein the lithium battery comprises the Silicon-based negative electrode material containing the skeleton structure of claim 1.

9. The lithium battery of claim 8, wherein the lithium battery is a liquid lithium ion battery, a semi-solid lithium ion battery, an all-solid ion battery or a lithium-sulfur battery.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The technical solution of the embodiments of the present disclosure will be described in further detail with reference to the drawings and embodiments.

[0033] FIG. 1 is an X-ray diffraction (XRD) diagram of a Silicon-based negative electrode containing a silicate skeleton provided in Embodiment 1 of the present disclosure after one cycle;

[0034] FIG. 2 is an XRD diagram of the Silicon-based negative electrode containing the silicate skeleton provided in Embodiment 1 of the present disclosure after 50 cycles;

[0035] FIG. 3 is a scanning electron microscope (SEM) diagram of Silicon-based negative electrode particles containing the silicate skeleton provided in Embodiment 1 of the present disclosure;

[0036] FIG. 4 is an XRD diagram of a Silicon-based negative electrode containing a silicate skeleton provided in Embodiment 2 of the present disclosure after one cycle; and

[0037] FIG. 5 is an XRD diagram of the Silicon-based negative electrode containing the silicate skeleton provided in Embodiment 2 of the present disclosure after 50 cycles.

DETAILED DESCRIPTION

[0038] The present invention will be further explained below with reference to drawings and specific embodiments, but it should be understood that these embodiments are only for more detailed explanation, and should not be construed as limiting the present disclosure in any way, that is, not intended to limit the scope of protection of the present disclosure.

[0039] A Silicon-based negative electrode material containing a silicate skeleton provided by the present disclosure comprises a modified SiO.sub.x material with a silicate material dispersed inside; [0040] the general formula of the modified SiO.sub.x material with a silicate material dispersed inside is M.sub.xSiO.sub.y, 1 ≤ x < 6, 3 ≤ y < 6, the element M is one or more of Mg, Ni, Cu, Zn, Al, Na, Ca, K, Li, Fe and Co, the grain size of the modified SiO.sub.x material is 0.5-100 nm, preferably 2-30 nm, and in the modified SiO.sub.x material, the silicate material accounts for 5-60% of the total mass of the modified SiO.sub.x material, preferably 10-30%; and [0041] the dispersed silicate material constitutes a skeleton structure of the Silicon-based negative electrode material, does not have physical and chemical reactions with lithium intercalation and deintercalation of the Silicon-based negative electrode material during the cycling process, and keeps the original structure even after multiple cycles.

[0042] Further, the Silicon-based negative electrode material may also comprise a carbon coating layer, and the modified SiO.sub.x material is coated with the carbon coating layer with a thickness of 1-100 nm.

[0043] The average particle diameter (D.sub.50) of the Silicon-based negative electrode material of the present disclosure is 0.1-40 .Math.m, and the specific surface area is 0.5-40 m.sup.2/g. In a preferred embodiment, the average particle diameter (D.sub.50) is 2-15 .Math.m, and the specific surface area is 1-10 m.sup.2/g.

[0044] The dispersion of different silicates corresponds to different structures and morphologies of internal molecules of the obtained Silicon-based negative electrode material.

[0045] When the element M is Mg, the corresponding silicate is MgSiO.sub.3 and/or Mg.sub.2SiO.sub.4, maximum X-ray diffraction (XRD) peaks of MgSiO.sub.3 are located at one or more of 28.1 degrees, 31.1 degrees, 34.8 degrees, 34.9 degrees and 36.9 degrees, and a maximum XRD peak of Mg.sub.2SiO.sub.4 is located at 36.5 degrees; [0046] when the element M is Ni, the corresponding silicate is NiSiO.sub.4, and a maximum XRD peak of NiSiO.sub.4 is located at 37.0 degrees; [0047] when the element M is Cu, the corresponding silicate is CuSiO.sub.3, and a maximum XRD peak of CuSiO.sub.3 is located at 12.2 degrees; [0048] when the element M is Zn, the corresponding silicate is ZnSiO.sub.3 and/or Zn.sub.2SiO.sub.4, maximum XRD peaks of ZnSiO.sub.3 are located at 31.0 degrees and/or 34.0 degrees, and maximum XRD peaks of Zn.sub.2SiO.sub.4 are located at one of more of (31.0 degrees and 34.0 degrees), 31.5 degrees, 31.7 degrees, 33.1 degrees, 36.5 degrees and 37.0 degrees; [0049] when the element M is Al, the corresponding silicate is Al.sub.2SiO.sub.5, and a maximum XRD peak of Al.sub.2SiO.sub.5 is located at 26.1 degrees and/or 28.0 degrees; [0050] when the element M is Na, the corresponding silicate is Na.sub.2SiO.sub.3 and/or Na.sub.4SiO.sub.4, a maximum XRD peak of Na.sub.2SiO.sub.3 is located at 29.4 degrees, and maximum XRD peaks of Na.sub.4SiO.sub.4 are located at 13.0 degrees and 23.2 degrees; [0051] when the element M is Ca, the corresponding silicate is CaSiO.sub.3 and/or Ca.sub.2SiO.sub.4, maximum XRD peaks of CaSiO.sub.3 are located at 25.3 degrees and/or 30.0 degrees, and maximum XRD peaks of Ca.sub.2SiO.sub.4 are located at one of more of 32.0 degrees, 32.1 degrees, 32.5 degrees, 32.7 degrees, 32.8 degrees, 33.0 degrees and 33.2 degrees; [0052] when the element M is K, the corresponding silicate is K.sub.4SiO.sub.4, and maximum XRD peaks of K.sub.4SiO.sub.4 are located at 30.4 degrees and 37.8 degrees; [0053] when the element M is Li, the corresponding silicate is Li.sub.2SiO.sub.3 and/or Li.sub.4SiO.sub.4, maximum XRD peaks of Li.sub.2SiO.sub.3 are located at 18.9 degrees and/or 27.0 degrees, and maximum XRD peaks of Li.sub.4SiO.sub.4 are located at (22.2 degrees and 33.8 degrees) and/or 34.9 degrees; [0054] when the element M is Fe, the corresponding silicate is FeSiO.sub.3 and/or Fe.sub.2SiO.sub.4, a maximum XRD peak of FeSiO.sub.3 is located at 32.7 degrees, and a maximum XRD peak of Fe.sub.2SiO.sub.4 is located at 63.8 degrees; and [0055] when the element M is Co, the corresponding silicate is Co.sub.2SiO.sub.4, and maximum XRD peaks of Co.sub.2SiO.sub.4 are located at 36.4 degrees, 36.5 degrees and 36.6 degrees.

[0056] The Silicon-based negative electrode material mentioned above can be used in negative electrode plates and lithium ion batteries, such as liquid lithium ion batteries, semi-solid lithium ion batteries, all-solid ion batteries or lithium-sulfur batteries, and can also be combined with other materials to serve as a negative electrode material in practice.

[0057] According to the Silicon-based negative electrode material containing the silicate skeleton provided by the present disclosure, the SiO.sub.x material is modified by introducing the silicate material into the traditional SiO.sub.x material in a dispersing manner, so that the modified material can be used as a Silicon-based negative electrode material. The dispersed silicate material has is stable in structure and property, and does not have physical and chemical reactions with lithium intercalation and deintercalation of the material. The silicate material constitutes the skeleton structure of the Silicon-based negative electrode material, and the silicate skeleton can generate a pinning effect on the volume expansion of the Silicon-based negative electrode, so as to alleviate deformation stress, and improve the cycling performance of the material.

[0058] In order to better understand the technical scheme provided by the present disclosure, several specific examples are given below to illustrate Silicon-based negative electrode materials containing different silicate skeletons, application methods thereof in lithium ion batteries and battery characteristics.

Embodiment 1

[0059] (1) SiO.sub.x powder, magnesium metasilicate powder and magnesium silicate powder were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0060] (2) the mixture was subjected to heat treatment at 1400° C. for hours in vacuum, and then cooled, crushed and screened; [0061] (3) the screened sample was mixed with petroleum asphalt according to the mass ratio of 20:1, and the mixture was placed in a high-temperature furnace to be subjected to heat treatment at 900° C. in a nitrogen atmosphere for 2 hours to obtain a Silicon-based negative electrode containing a magnesium metasilicate and magnesium silicate skeleton; [0062] According to the solid-solid mixing method, silicate firstly adhered to surfaces of SiO.sub.x particles, and then high-temperature treatment was conducted, so that the silicate can quickly diffuse into the SiO.sub.x particles to form a skeleton structure under the driving of its own concentration difference; [0063] (4) the Silicon-based negative electrode containing the magnesium metasilicate and magnesium silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, the ternary positive electrode material, Lithium nickel cobalt manganate NCM 333, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1; [0064] (5) discharged batteries were disassembled after one cycle and 50 cycles, a negative electrode plate was soaked and washed with a dimethyl carbonate (DMC) solvent, an electrode sheet material was scraped off after air-drying for an XRD test, and the XRD diagrams obtained are shown in FIGS. 1 and 2; and it can be clearly seen in the figures that the material contains MgSiO.sub.3 and Mg.sub.2SiO.sub.4, with the main peaks at 31.1 degrees and 36.5 degrees respectively, and after 50 cycles, XRD peaks of the MgSiO.sub.3 and Mg.sub.2SiO.sub.4 skeleton did not change; and [0065] (6) the SEM diagram of the carbon-coated Silicon-based negative electrode particles containing the magnesium metasilicate and magnesium silicate skeleton obtained in this embodiment is shown in FIG. 3.

Embodiment 2

[0066] (1) SiO.sub.x powder and magnesium metasilicate powder were uniformly mixed according to the mass ratio of 3:1, and placed in a vacuum furnace; [0067] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0068] (3) a screened sample was placed in a rotary furnace, a mixed gas of argon and methane with a volume ratio of 3:1 was introduced at 1000° C., and the temperature was kept for 2 hours to obtain a Silicon-based negative electrode containing a magnesium metasilicate skeleton; [0069] (4) the Silicon-based negative electrode containing the magnesium metasilicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a positive electrode material, lithium cobaltate (LCO), was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1; [0070] (5) discharged batteries were disassembled after one cycle and 50 cycles, a negative electrode plate was soaked and washed with a DMC solvent, an electrode sheet material was scraped off after air-drying for an XRD test, and the XRD diagrams obtained are shown in FIGS. 4 and 5; and it can be clearly seen in the figures that the material contains MgSiO.sub.3, with the main peak at 31.1 degrees, and after 50 cycles, XRD peaks of the MgSiO.sub.3 skeleton did not change.

Embodiment 3

[0071] (1) SiO.sub.x powder and nickel silicate were uniformly mixed according to the mass ratio of 3:1, and placed in a vacuum furnace; [0072] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0073] (3) a screened sample was placed in a rotary furnace, a mixed gas of argon and acetylene with a volume ratio of 2:1 was introduced at 950° C., and the temperature was kept for 2 hours to obtain a Silicon-based negative electrode containing a nickel silicate skeleton; [0074] (4) the Silicon-based negative electrode containing the nickel silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, the ternary positive electrode material, Lithium nickel cobalt manganate NCM 523, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 4

[0075] (1) SiO.sub.x powder and copper metasilicate powder were uniformly mixed according to the mass ratio of 3:1, and placed in a vacuum furnace; [0076] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0077] (3) a screened sample and phenolic resin were dissolved in an alcohol solvent according to the ratio of 20:1, and stirred for 6 hours to form uniform slurry; [0078] (4) the above slurry was directly dried; [0079] (5) the dried slurry was placed in a high-temperature furnace, and the mixture was sintered at 900° C. for 2 hours in a nitrogen protection atmosphere, and then cooled, crushed and screened to obtain a Silicon-based negative electrode containing a copper metasilicate skeleton; [0080] (6) the Silicon-based negative electrode containing the copper metasilicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a ternary positive electrode material, Lithium nickel cobalt aluminate NCA, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 5

[0081] (1) SiO.sub.x powder, zinc metasilicate powder and zinc silicate powder were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0082] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0083] (3) a screened sample was mixed with glucose powder according to the ratio of 20:1, and the mixture was placed in a high-temperature furnace to be sintered at 900° C. in an argon protection atmosphere for 2 hours to obtain a Silicon-based negative electrode containing a zinc metasilicate and zinc silicate skeleton; [0084] (4) the Silicon-based negative electrode containing the zinc metasilicate and zinc silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a positive electrode material, lithium manganese oxide (LMO), was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 6

[0085] (1) SiO.sub.x powder and aluminum silicate were uniformly mixed according to the mass ratio of 3:1, and placed in a vacuum furnace; [0086] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0087] (3) the screened sample and polyvinylidene fluoride (PVDF) were dissolved in an N,N-dimethylformamide (DMF) solvent according to the ratio of 20:1, and stirred for 6 hours to form uniform slurry; [0088] (4) the above slurry was directly dried; [0089] (5) the dried slurry was placed in a high-temperature furnace, and the mixture was sintered at 900° C. for 2 hours in an argon protection atmosphere, and then cooled, crushed and screened to obtain a Silicon-based negative electrode containing an aluminum silicate skeleton; [0090] (6) the Silicon-based negative electrode containing the aluminum silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7:2:1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a ternary positive electrode material, NCM 811, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 7

[0091] (1) SiO.sub.x powder, sodium metasilicate powder and sodium silicate powder were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0092] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0093] (3) a screened sample was placed in a rotary furnace, a mixed gas of argon and acetylene with a volume ratio of 2:1 was introduced at 950° C., and the temperature was kept for 2 hours to obtain a Silicon-based negative electrode containing a sodium metasilicate and sodium silicate skeleton; [0094] (4) the Silicon-based negative electrode containing the sodium metasilicate and sodium silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a positive electrode material, lithium cobaltate (LCO), was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 8

[0095] (1) SiO.sub.x powder, calcium metasilicate powder and calcium silicate powder were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0096] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0097] (3) a screened sample was placed in a rotary furnace, a mixed gas of argon and methane with a volume ratio of 3:1 was introduced at 1000° C., and the temperature was kept for 2 hours to obtain a Silicon-based negative electrode containing a calcium metasilicate and calcium silicate skeleton; [0098] (4) the Silicon-based negative electrode containing the calcium metasilicate and calcium silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a positive electrode material, lithium cobaltate (LCO), was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 9

[0099] (1) SiO.sub.x powder and potassium silicate were uniformly mixed according to the mass ratio of 3:1, and placed in a vacuum furnace; [0100] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0101] (3) the screened sample was mixed with petroleum asphalt according to the mass ratio of 20:1, and the mixture was placed in a high-temperature furnace to be subjected to heat treatment at 900° C. in a nitrogen atmosphere for 2 hours to obtain a Silicon-based negative electrode containing a potassium silicate skeleton; [0102] (4) the Silicon-based negative electrode containing the potassium silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7:2:1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, the ternary positive electrode material, NCM 333, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 10

[0103] (1) SiO.sub.x powder, lithium metasilicate powder and lithium silicate powder were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0104] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0105] (3) the screened sample was mixed with petroleum asphalt according to the mass ratio of 20:1, and the mixture was placed in a high-temperature furnace to be subjected to heat treatment at 900° C. in a nitrogen atmosphere for 2 hours to obtain a Silicon-based negative electrode containing a lithium metasilicate and lithium silicate skeleton; [0106] (4) the Silicon-based negative electrode containing the lithium metasilicate and lithium silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7:2:1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, the ternary positive electrode material, NCM 333, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 11

[0107] (1) SiO.sub.x powder, ferric metasilicate powder and ferric silicate powder were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0108] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0109] (3) a screened sample was placed in a rotary furnace, a mixed gas of argon and methane with a volume ratio of 3:1 was introduced at 1000° C., and the temperature was kept for 2 hours to obtain a Silicon-based negative electrode containing a ferric metasilicate and ferric silicate skeleton; [0110] (4) the Silicon-based negative electrode containing the ferric metasilicate and ferric silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a positive electrode material, lithium cobaltate (LCO), was used as a counter electrode, garnet type Li.sub.7La.sub.3Zr.sub.2O.sub.12(LLZO) was used as a solid electrolyte, a solid button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

Embodiment 12

[0111] (1) SiO.sub.x powder, Cobalt metasilicate powder, and cobaltous silicate were uniformly mixed according to the mass ratio of 3:0.3:0.7, and placed in a vacuum furnace; [0112] (2) the mixture was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0113] (3) a screened sample was placed in a rotary furnace, a mixed gas of argon and methane with a volume ratio of 3:1 was introduced at 1000° C., and the temperature was kept for 2 hours to obtain a Silicon-based negative electrode containing a cobaltous silicate skeleton; [0114] (4) the Silicon-based negative electrode containing the cobaltous silicate skeleton, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, a positive electrode material, lithium cobaltate (LCO), was used as a counter electrode, a polyolefin-based gel polymer electrolyte membrane was used as a semi-solid electrolysis, a semi-solid button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

[0115] For convenience of explanation, the present disclosure also provides a comparative example.

Comparative Example 1

[0116] (1) SiO.sub.x powder was placed in a vacuum furnace; [0117] (2) the SiO.sub.x powder was subjected to heat treatment at 1400° C. for 2 hours in vacuum, and then cooled, crushed and screened; [0118] (3) a screened sample was mixed with petroleum asphalt according to the mass ratio of 20:1 the mixture was placed in a high-temperature furnace to be subjected to heat treatment at 900° C. in a nitrogen atmosphere for 2 hours; and [0119] (4) an obtained Silicon-based negative electrode, carbon black (SP) and sodium carboxymethyl cellulose (CMC) were mixed according to the ratio of 7: 2: 1 to prepare negative electrode slurry, a negative electrode plate was prepared after coating and drying, the ternary positive electrode material, NCM 333, was used as a counter electrode, a button cell was assembled in a glove box, a charging and discharging test was conducted, and then cycling performance was evaluated; results are shown in Table 1.

TABLE-US-00001 Embodiment First-cycle efficiency % 50-cycle capacity retention rate % 1 83.91 52.8 2 83.53 50.3 3 82.88 52.2 4 83.67 52.2 5 82.50 52.0 6 82.43 51.3 7 83.66 53.6 8 82.73 44.9 9 83.62 46.2 10 83.82 51.8 11 83.73 40.3 12 83.88 42.9 Comparative example 1 79.50 21.2

[0120] Table 1 above shows the comparison of the electrochemical cycling performance of lithium secondary batteries prepared in Embodiments 1-12 and Comparative Example 1. By comparison, it can be seen that in the embodiments, phosphate was dispersed in a matrix of the Silicon-based negative electrode, which plays a role of supporting the skeleton, and no physical and chemical reaction occurred during electrochemical lithium intercalation and deintercalation. This stable structure provides skeleton support for the Silicon-based negative electrode, and alleviates stress and strain caused by volume expansion, so that the 50-cycle capacity retention rate of each embodiment is greatly improved compared with the comparative example, that is, the cycling performance of the silicon-based negative electrode is effectively improved.

[0121] The above-mentioned specific embodiments further explain the purpose, technical scheme and beneficial effects of the present disclosure in detail. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the scope of protection of the present disclosure. Any modification, equivalent substitution, improvement, etc., made within the spirit and principles of the present disclosure should be included in the scope of protection of the present disclosure.