Patent Description:
Lithium-ion secondary batteries are widely used in portable electronic products, electric vehicles and energy storage. However, during the initial charge, electrolyte is unstable and forms a SEI film on the surface of electrodes, consuming a large amount of lithium, resulting in low initial coulombic efficiency. For graphite, <NUM>-<NUM>% of lithium is used to form the SEI film in the first cycle, while Si, Sn and SiOx need to consume <NUM>-<NUM>% of lithium. In this regard, researchers have made a series of optimized designs, such as preparation of nanowires, porous nanostructures and carbon coating and the like. Although the cycling performance is improved, the contact area with the electrolyte is increased, the initial efficiency is reduced, cathode material is consumed in large amount, and energy density is lowered. Obviously, it is imperative to carry out lithium supplement to anode materials in advance.

At present, there are mainly three methods for doping SiOx with lithium: directly coating a lithium layer on the surface of pole pieces, electrochemically plating lithium on the surface of pole pieces, or mixing SiOx with a lithium compound followed by calcination. The lithium source selected is mainly concentrated on metallic lithium, and some have tried LiOH and LiH.

<CIT> discloses a lithium-containing silicon oxide powder and a production method thereof, which comprises calcining a mixture of raw material powder capable of producing SiO gas with metallic lithium or lithium compound powder at <NUM> to <NUM> to obtain a lithium-containing silicon oxide powder, which can increase the capacity and the initial efficiency of the material. However, the introduction of a lithium source during the synthesis stage of raw materials greatly promotes growth of Si grains and reduces cycling.

<CIT> discloses a method for preparing a silicon / lithium-rich phase composite anode material for lithium secondary battery by high-energy ball milling, in which silicon monoxide and metallic lithium are high-energy ball milled, and then heat-treated in vacuum to obtain the silicon / lithium-rich phase composite anode material, with its specific capacity and cycling improved. However, the Li<NUM>O produced by directly reacting bare silicon monoxide with metallic lithium is easy to absorb moisture and react, which affects the late stability of the material, and makes mass production difficult to achieve.

<CIT> discloses an anode material for electricity storage devices and a preparation method thereof. In the presence of a solvent, a Si-based material capable of occluding and releasing lithium ions is blended with a lithium metal by mixing, and then heat-treated to form lithium silicate to produce an anode material pre-doped with lithium. However, the produced lithium silicate phase that is not subjected to secondary treatment shows strong alkalinity, and it is difficult to process in the later stage and cannot be used in bulk.

<CIT> describes an electrode active material for a secondary battery, which comprises a porous silicon oxide-based composite.

<CIT> describes a negative electrode active material containing particles made of SiOX containing a lithium silicate phase, where <NUM>% to <NUM>% of the surface of each particle made of SiOX is covered by carbon.

<CIT> describes a negative electrode material comprising a silicon-silicon oxide composite and a carbon coating formed on a surface of the silicon-silicon oxide composite, wherein at least the silicon-silicon oxide composite is doped with lithium.

<CIT> describes surface-modified silicon nanoparticles comprising a LixSiyOz top film and a carbon (C) coating layer on the surface of the nanoparticles.

<CIT> describes a negative electrode active material particle having a lithium silicate phase represented by Li2zSiO(<NUM>+z) {<NUM> < z < <NUM>} and silicon particles dispersed in the lithium silicate phase.

<CIT> describes a negative electrode having a carbonaceous material, composite particles comprising a silicon oxide dispersed in the carbonaceous material, silicon dispersed in the silicon oxide, a lithium silicate phase contained in the silicon oxide and containing Li<NUM>SiO<NUM> as the main component.

<CIT> describes a negative-electrode active material, which includes a first chemical element composed of lithium, silicon or tin and a second chemical element composed of oxygen or fluorine.

<CIT> describes a process for producing a silicon, silicon oxide, lithium composite (SSLC) material for use as a negative electrode active material for non-aqueous battery cells.

The following is a summary of the subject matter that is described in greater detail by the present disclosure. The summary is not intended to be limiting as to the protection scope of the claims.

It's an object of the present disclosure to provide a composite, a preparation method thereof and an anode material and a lithium-ion secondary battery comprising the same. The method of the present disclosure is simple, and has low requirements on equipments and low cost, and the composite obtained therefrom has a stable structure, which can effectively avoid the failure of active ingredients due to infiltration of components such as air into the interior of particles, and the structure and properties of the composite do not deteriorate during long-term storage. A battery made of the anode material containing the composite exhibits high delithiation capacity, high initial coulombic efficiency and good cycling performance, which has a charge capacity of <NUM> mAh/g or more, a discharge capacity of <NUM> mAh/g or more and an initial efficiency of <NUM>% or more.

In order to achieve the above object, the present disclosure adopts the following technical solutions:
In a first aspect, the present disclosure provides a Si-O-C-Li composite, which comprises nano-silicon, a silicon-oxygen-lithium compound, silicon oxide and a carbon coating, wherein the silicon-oxygen-lithium compound is partially crystalline, and the nano-silicon and the silicon-oxygen-lithium compound are grown from in-situ reduction of a carbon-coated silicon oxide which comprises a silicon oxide and a carbon coating coated on the surface of the silicon oxide such that there is no clear interface between the nano-silicon and the silicon-oxygen-lithium compound; and
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, and the fusion particles are dispersed in the silicon oxide as a matrix in a sea-island form to form composite particles, with the carbon coating coated on the surface of the composite particles.

In this preferred technical solution, the silicon oxide has a chemical composition of SiOx, in which <NUM><x<<NUM>. Wherein, x may possess a value of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like.

In the present disclosure, a carbon-coated silicon oxide and a reducing agent are used as raw materials. Through the steps such as primary treatment and heat treatment and the like, the reducing agent undergoes a redox reaction with the silicon oxide in the interior of the carbon coating, and nano-silicon is grown from in-situ reduction, and a silicon-oxygen-lithium compound is produced.

In the present disclosure, since the nano-silicon is grown from in-situ reduction of a carbon-coated silicon oxide, there is no clear interface between the nano-silicon and the silicon-oxygen-lithium compound obtained by the reaction, and this structural feature is closely related to the preparation method of the present disclosure.

The method of the present disclosure can effectively reduce or even avoid the agglomeration problem among nano-silicons, thereby reducing the silicon expansion problem in the process of application to a battery, and improving the cycle life of the battery.

The nano-silicon of the present disclosure has a diameter in nanoscale.

In the present disclosure, the composite has such a structure that: nano-silicon is dispersed in the silicon-oxygen-lithium compound to form fusion particles, and the fusion particles are dispersed in the silicon oxide served as a matrix in a sea-island form to form composite particles, with the carbon coating coated on the surface of the composite particles (see <FIG> for a schematic structural view of the composite).

In the present disclosure, the expression "the fusion particles are dispersed in the silicon oxide served as a matrix in a sea-island form" means that all directions of the fusion particles are surrounded by the silicon oxide that is served as a matrix.

Preferably, the silicon-oxygen-lithium compound comprises any one selected from the group consisting of Li<NUM>SiO<NUM>, Li<NUM>SiO<NUM>, Li<NUM>Si<NUM>O<NUM>, Li<NUM>Si<NUM>O<NUM>, and a mixture of at least two selected therefrom; e.g. a mixture of Li<NUM>SiO<NUM> and Li<NUM>SiO<NUM>, a mixture of Li<NUM>SiO<NUM> and Li<NUM>Si<NUM>O<NUM>, a mixture of Li<NUM>SiO<NUM> and Li<NUM>Si<NUM>O<NUM>, a mixture of Li<NUM>SiO<NUM>, Li<NUM>Si<NUM>O<NUM> and Li<NUM>Si<NUM>O<NUM> and the like.

Preferably, the carbon coating has a thickness of <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like, preferably <NUM>-<NUM>.

Preferably, the carbon coating contains hard carbon.

Preferably, 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.

Preferably, based on <NUM> wt% of the total mass of the carbon coating, the carbon nanotubes and/or graphene sheets in the carbon coating have a mass percent of <NUM>-<NUM> wt%, e.g. <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt% or <NUM> wt% and the like.

Preferably, based on <NUM> wt% of the total mass of the composite, the carbon coating has a mass percent of <NUM>-<NUM> wt%, e.g. <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt% or <NUM> wt% and the like, further preferably <NUM>-<NUM> wt%.

The composite provided by the present disclosure is structurally stable during long-term storage in air, and the "long-term" means that the time is <NUM> days or more.

In a second aspect, the present disclosure provides a method of preparing the composite according to the first aspect, and the method comprises the following steps:.

wherein in step (<NUM>) of the present disclosure, 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.

The method of the present disclosure can effectively reduce or even avoid the agglomeration problem among nano-silicons, thereby reducing the silicon expansion problem in the process of application to batteries, and improving the cycle life of the batteries.

The step of surface treatment can remove the residual lithium or lithium-containing compound on the surface of the composite obtained in the step (<NUM>), or compound the residual lithium or lithium-containing compound on the surface to the interior.

The manner in which the residual lithium or the lithium-containing compound can be removed, such as impurity removal mode (washing or impregnation, and the like), for example, may be performed by impregnating the composite into the impurity removing solution.

The manner in which the residual lithium or the lithium-containing compound can be compounded to the interior is exemplified as coating, cladding, film plating or spraying and the like. The substance coated, cladded, film plated or sprayed may be but not limited to a carbon layer, a polymer and the like.

Preferably, the silicon oxide has a chemical composition of SiOx, in which <NUM><x<<NUM>, exemplarily, x may possess a value of <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like.

Preferably, the carbon coating has a thickness of <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like, preferably <NUM>-<NUM>.

The "carbon nanotubes and/or graphene sheets" as used in the present disclosure means that it may be carbon nanotubes, graphene sheets, or a mixture of carbon nanotubes and graphene sheets.

Preferably, the organic carbon source comprises any one selected from the group consisting of phenolic resin, epoxy resin, polyurethane, asphalt, coal tar, polythiophene, polyolefin, saccharides, polyhydric alcohols, phenolic resin derivatives, epoxy resin derivatives, polyurethane derivatives, asphalt derivatives, coal tar derivatives, polythiophene derivatives, saccharides derivatives, polyhydric alcohols derivatives, and a combination of at least two selected therefrom.

Preferably, the temperature of the carbonization treatment is <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like, preferably <NUM>-<NUM>.

Preferably, the time for the carbonization treatment is <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like, preferably <NUM>-<NUM>.

Preferably, based on <NUM> wt% of the total mass of the carbon coating, the carbon nanotubes and/or graphene sheets in the carbon coating has a mass percent of <NUM>-<NUM> wt%, e.g. <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt%, <NUM> wt% or <NUM> wt% and the like.

Preferably, in the carbon-coated silicon oxide in step (<NUM>), the mass ratio of the silicon oxide to the carbon coating is <NUM>:(<NUM>-<NUM>), e.g. <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM> or <NUM>:<NUM> and the like.

Preferably, the lithium source in step (<NUM>) is lithium-containing compound with strong alkalinity, lithium-containing compound with reducibility, or elemental lithium, in which "lithium-containing compound with strong alkalinity" means that <NUM> of the aqueous solution of the lithium-containing compound has a pH greater than <NUM>, e.g. LiNH<NUM>, Li<NUM>CO<NUM>, lithium oxide, lithium metal, lithium hydride, lithium hydroxide, lithium acetate, lithium oxalate, lithium formate, phenyl lithium, alkyl lithium, t-butyl lithium, n-butyl lithium or lithium t-butoxide and the like. However, it does not limit to the above-listed substances, other substances which can achieve the same effect can also be used in the present disclosure.

Preferably, the mass ratio of the carbon-coated silicon oxide to the lithium source in step (<NUM>) is <NUM>:(<NUM>-<NUM>), preferably <NUM>:(<NUM>-<NUM>), e.g. <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>: <NUM> or <NUM>:<NUM> and the like.

Preferably, the solid-phase mixing mode in step (<NUM>) 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.

Preferably, the time for the blending in step (<NUM>) is <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like.

Preferably, the mixing is performed in vacuum condition.

Preferably, the apparatus used for the dispersion is a high-speed disperser.

The step (<NUM>) of the present disclosure comprises blending in solid-phase mixing mode, so that the lithium source is sufficiently contacted with the carbon-coated silicon oxide, and the dispersion is more uniform, and primary treatment is implemented to obtain a pre-lithium precursor.

Preferably, the non-oxidizing atmosphere in step (<NUM>) 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 (<NUM>) is <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like, preferably <NUM>-<NUM>, further preferably <NUM>-<NUM>.

The time for the heat-treating in step (<NUM>) is <NUM>-<NUM>, e.g. <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> and the like, preferably <NUM>-<NUM>.

In the present disclosure, via the heat treatment in vacuum or non-oxidizing atmosphere in step (<NUM>), 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 generate a silicon-oxygen-lithium compound, so that the substance species in the interior of the carbon coating are adjusted, moreover, the adjustment of the product structure is also achieved to obtain the composite of the present disclosure (which is a Si-O-C-Li composite).

Preferably, a surface treatment of the composite is continued, to obtain a surface-treated composite (which is also a Si-O-C-Li composite).

When the composite comprises nano-silicon, a silicon oxide, a silicon-oxygen-lithium compound and a carbon coating, it indicates that the silicon oxide in the raw material carbon-coated silicon oxide is not completely reacted, with surplus silicon oxide.

In a third aspect, the present disclosure provides an anode material, which comprises the composite according to the first aspect.

In a fourth aspect, the present disclosure provides a use of the composite according to the first aspect in lithium-ion secondary batteries.

The lithium-ion secondary battery comprises the anode material according to the third aspect. The anode material may be used in combination with a carbon material capable of intercalating and deintercalating lithium ions.

As compared to the prior art, the present disclosure has the following beneficial effects:.

The technical solutions of the present disclosure will be further described below in conjunction with the accompanying drawings and specific embodiments.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium source LiNH<NUM> were high-speed dispersed until homogeneously mixed; then the mixture was heat treated at <NUM> for <NUM> in an argon atmosphere, naturally cooled to room temperature to take out a composite. Then impurity removal was performed by means of impregnation, and the composite was dried to obtain a surface-treated composite.

<FIG> is a SEM image of the composite obtained in the present example. It can be seen from the figure that dark regions formed by a nano-silicon inlaid silicon-oxygen-lithium compound were uniformly distributed in the particle, which formed a sea-island structure in which the silicon-oxygen-lithium compound inlaid with nano-silicon was served as islands, and silicon oxide was served as the sea.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium source Li<NUM>CO<NUM> were high-speed dispersed until homogeneously mixed; then the mixture was heat treated at <NUM> for <NUM> in an argon atmosphere, naturally cooled to room temperature to take out a composite. Then impurity removal was performed by means of impregnation, and the composite was dried to obtain a surface-treated composite.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium metal powder as a lithium source were mixed in a vacuum state for <NUM>; then the mixture was heat treated at <NUM> for <NUM> in an argon atmosphere, naturally cooled to room temperature to take out a composite. Then impurity removal was performed by means of impregnation, and the composite was dried to obtain a surface-treated composite.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium oxide powder as a lithium source were mixed in a vacuum state for <NUM>; then the mixture was heat treated at <NUM> for <NUM> in an argon atmosphere, naturally cooled to room temperature to take out a composite. Then impurity removal was performed by means of impregnation, and the composite was dried to obtain a surface-treated composite.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium metal powder as a lithium source were ball milled for <NUM>; then the mixture was heat treated at <NUM> for <NUM> in an argon atmosphere, naturally cooled to room temperature to take out a composite. Then impurity removal was performed by means of impregnation, and the composite was dried to obtain a surface-treated composite.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium source LiNH<NUM> were high-speed dispersed until homogeneously mixed; then the mixture was heat treated at <NUM> for <NUM> in a nitrogen atmosphere, naturally cooled to room temperature to take out a composite. Then impurity removal was performed by means of impregnation, and the composite was dried to obtain a surface-treated composite.

<NUM> of SiOx (x=<NUM>) with carbon coating on the surface and <NUM> of lithium source Li<NUM>CO<NUM> were VC mixed for <NUM>; then the mixture was heat treated at <NUM> for <NUM> in an argon atmosphere, naturally cooled to room temperature to take out a composite. Then a layer of polymer film was sprayed on the surface of the composite, filtered and dried to obtain a surface-treated composite.

<NUM> of SiO was mixed with <NUM> of citric acid homogeneously, and then the mixture was fired in a nitrogen atmosphere box-type furnace at a firing temperature of <NUM>. After <NUM> of heat preservation, a SiO raw material having a carbon coating layer was obtained by naturally cooling to room temperature.

The anode materials for lithium ion batteries prepared in Examples <NUM>-<NUM> and the Comparative Example were used as active materials respectively, and PI was used as a binder. After conductive carbon black was added, a slurry was obtained by stirring and then coated on a copper foil, and finally anode plates were obtained by oven drying and rolling, wherein active material : conductive agent : binder = <NUM>:<NUM>:<NUM>. Lithium metal sheet was used as the counter electrode, PP/PE was used as the diaphragm, LiPF<NUM>/EC+DEC+DMC (the volume ratio of EC, DEC and DMC is <NUM>:<NUM>:<NUM>) was used as the electrolyte, and simulated batteries were assembled in a glove box filled with argon. The electrochemical performances of the batteries were tested with a LAND or Xinwei 5V/10mA battery tester, in which the charge-discharge voltage was set as <NUM>. 5V and the charge-discharge rate was set as <NUM>. 1C, and the test results were shown in Table <NUM>.

Claim 1:
A composite, which is a Si-O-C-Li composite comprising nano-silicon (<NUM>), a silicon-oxygen-lithium compound (<NUM>), silicon oxide (<NUM>) and a carbon coating (<NUM>), wherein the silicon-oxygen-lithium compound is partially crystalline, and the nano-silicon and the silicon-oxygen-lithium compound are grown from in-situ reduction of a carbon-coated silicon oxide which comprises a silicon oxide and a carbon coating coated on the surface of the silicon oxide such that there is no clear interface between the nano-silicon and the silicon-oxygen-lithium compound; and
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, and the fusion particles are dispersed in the silicon oxide as a matrix in a sea-island form to form composite particles, with the carbon coating coated on the surface of the composite particles.