Compound, preparation method therefore, and use in lithium ion secondary battery
Disclosed in the present application is a compound, comprising nano silicon, a lithium-containing compound and a carbon coating, or comprising nano silicon, silicon oxide, a lithium-containing compound, and a carbon coating. The method comprises: (1) solid-phase mixing of carbon coated silicon oxide with a lithium source; and (2) preforming heat-treatment of the pre-lithium precursor obtained in step ( 1 ) in a vacuum or non-oxidising atmosphere to obtain a compound. The method is simple, and has low equipment requirements and low costs; the obtained compound has a stable structure and the structure and properties do not deteriorate during long-term storage, a battery made of cathode material containing said compound exhibits high delithiation capacity, high initial coulombic efficiency, and good recycling properties, the charging capacity is over 1920 mAh/g, the discharging capacity is over 1768 mAh/g, and the initial capacity is over 90.2%.
1. A composite, which is a Si—O—C—Li composite comprising nano-silicon, a silicon-oxygen-lithium compound selected from the group consisting of Li2SiO3, Li4SiO4, Li2Si2O5, Li2Si3O7 and combinations thereof, silicon oxide and a carbon coating,
wherein the silicon-oxygen-lithium compound is partially crystalline, the nano-silicon is dispersed in the silicon-oxygen-lithium compound to form fusion particles of the nano-silicon and the silicon-oxygen-lithium compound without clear interface between the nano-silicon and the silicon-oxygen-lithium compound, and the fusion particles are uniformly dispersed in the silicon oxide to form a composite particle wherein all directions of the fusion particles are surrounded by the silicon oxide matrix, forming a sea-island structure with the fusion particles as islands and with the silicon oxide as the sea, with the carbon coating coated on the surface of the composite particles;
wherein the nano-silicon and the silicon-oxygen-lithium compound are produced by in-situ redox growth.
2. The composite according to claim 1 , wherein the silicon oxide has a chemical composition of SiOx, in which 0<x<2.
3. The composite according to claim 1 , wherein the nano-silicon is grown from in-situ reduction of a carbon-coated silicon oxide, and the carbon-coated silicon oxide comprises a silicon oxide and a carbon coating coated on the surface of the silicon oxide.
4. The composite according to claim 1 , wherein the carbon coating comprises a carbon matrix and carbon nanotubes and/or graphene sheets embedded in the carbon matrix, and the carbon matrix is obtained by cracking an organic carbon source via carbonization treatment.
5. The composite according to claim 1 , wherein based on 100 wt % of the total mass of the composite, the carbon coating has a mass percent of 0.1-50 wt %.
6. A preparation method of a composite, wherein the composite is a Si—O—C—Li composite comprising nano-silicon, a silicon-oxygen-lithium compound selected from the group consisting of Li2SiO3, Li4SiO4, Li2Si2O5, Li2Si3O7 and combinations thereof, silicon oxide and a carbon coating:
wherein the silicon-oxygen-lithium compound is partially crystalline, the nano-silicon is dispersed in the silicon-oxygen-lithium compound to form fusion particles of the nano-silicon and the silicon-oxygen-lithium compound without clear interface between the nano-silicon and the silicon-oxygen-lithium compound, and the fusion particles are uniformly dispersed in the silicon oxide to form a composite particle wherein all directions of the fusion particles are surrounded by the silicon oxide matrix, forming a sea-island structure with the fusion particles as islands and with the silicon oxide as the sea, with the carbon coating coated on the surface of the composite particles; and
wherein the nano-silicon and the silicon-oxygen-lithium compound are produced by in-situ redox growth;
the preparation method comprises the following steps:
(1) blending a carbon-coated silicon oxide and a lithium source by solid-phase mixing mode to implement primary treatment to form a pre-lithium precursor; wherein the lithium source undergoes a redox reaction with the silicon oxide in the interior of the carbon coating, and in-situ redox growth results in nano-silicon and a silicon-oxygen-lithium compound, and there is no clear interface between the nano-silicon and the silicon-oxygen- lithium compound; wherein the solid-phase mixing mode comprises any one selected from the group consisting of ball milling, VC mixing, fusion, mixing, kneading, dispersion, or a combination of at least two selected therefrom, and the solid-phase mixing mode is performed in vacuum condition;
(2) heat-treating the pre-lithium precursor in vacuum or a non-oxidizing atmosphere to implement structural adjustment and secondary treatment to form the Si—O—C—Li composite according to any of claim 1 , wherein the lithium source infiltrates into the interior of the carbon-coated silicon oxide to react in situ with the silicon oxide to produce nano-silicon and the Si—O—C—Li composite, wherein the temperature of the heat-treating is 160-1000° C., and the time for the heat-treating is 2-12 h;
(3) subjecting the composite to surface treatment to compound the residual lithium or silicon-oxygen-lithium compound on the surface to the interior to obtain a surface- treated composite; the manner of compounding the residual lithium or the silicon-oxygen- lithium compound is any one selected from the group consisting of coating, cladding, film plating, spraying, and a combination of at least two selected therefrom; the manner of impurity removal is any one selected from the group consisting of washing, impregnation, and a combination of at least two selected therefrom, the washing or impregnation is carried out using an impurity removing solution.
7. The method according to claim 6 , further comprising step ( 3 ) of subjecting the composite to surface treatment after the heat treatment of step ( 2 ) to obtain a surface-treated composite.
8. The method according to claim 6 , wherein the lithium source in step ( 1 ) is any one selected from the group consisting of lithium-containing compound with strong alkalinity, lithium-containing compound with reducibility, elemental lithium, and a combination of at least two selected therefrom.
9. The method according to claim 6 , wherein the carbon-coated silicon oxide in step ( 1 ) comprises a silicon oxide and a carbon coating coated on the surface of the silicon oxide.
10. The method according to claim 9 , wherein the carbon coating comprises a carbon matrix and carbon nanotubes and/or graphene sheets embedded in the carbon matrix, and the carbon matrix is obtained by cracking an organic carbon source via carbonization treatment.
11. The method according to claim 10 , wherein the temperature of the carbonization treatment is 500-1300° C.;
the time for the carbonization treatment is 1-10 h.
12. The method according to claim 6 , wherein in the carbon-coated silicon oxide in step ( 1 ), the mass ratio of the silicon oxide to the carbon coating is 100:(2-15);
the mass ratio of the carbon-coated silicon oxide to the lithium source in step ( 1 ) is 1:(0.01-0.3).
13. The method according to claim 6 , wherein the solid-phase mixing mode in step ( 1 ) comprises any one selected from the group consisting of ball milling, VC mixing, fusion, mixing, kneading, dispersion, and a combination of at least two selected therefrom;
the time for the blending in step ( 1 ) is 2-12 h.
14. The method according to claim 6 , wherein the non-oxidizing atmosphere in step ( 2 ) comprises any one selected from the group consisting of hydrogen atmosphere, nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere, xenon atmosphere, and a combination of at least two selected therefrom;
the temperature of the heat-treating in step ( 2 ) is 160-1000° C.;
the time for the heat-treating in step ( 2 ) is 2-12 h.
15. The method according to claim 6 , wherein the manner of the surface treatment in step ( 3 ) comprises any one selected from the group consisting of impurity removal, cladding, surface functional group alteration, coating, film plating, spraying, and a combination of at least two selected therefrom.
16. A lithium-ion secondary battery comprising the composite according to claim 1 .