CN110380033A - A kind of core-shell material and preparation method thereof - Google Patents

A kind of core-shell material and preparation method thereof Download PDF

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Publication number
CN110380033A
CN110380033A CN201910659982.8A CN201910659982A CN110380033A CN 110380033 A CN110380033 A CN 110380033A CN 201910659982 A CN201910659982 A CN 201910659982A CN 110380033 A CN110380033 A CN 110380033A
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shell
layer
solution
dissolved
core
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Inventor
钟宽
李雪云
曾梦丝
吴西燚
魏文飞
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Gree Electric Appliances Inc of Zhuhai
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Gree Electric Appliances Inc of Zhuhai
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of core-shell materials and preparation method thereof, wherein core-shell material, comprising: core, the core contain Si oxide and titanium oxide；First layer shell, the first layer shell coat the core, and the first layer shell contains carbon simple substance；With second layer shell, the second layer shell coats the first layer shell, and two layers of shell contains Si oxide and titanium oxide.The core-shell material has high active component content.

Description

A kind of core-shell material and preparation method thereof
Technical field
The present invention relates to field of energy source materials, and in particular to a kind of core-shell material and preparation method thereof.
Background technique
Lithium ion battery has that energy density is high, voltage is high, have extended cycle life, big multiplying power discharging, self discharge are low, environmentally friendly etc. Advantage has been widely used in the field 3C, electric car and energy storage field.High-energy density is the master of lithium ion battery Want developing direction.Lithium ion battery with high energy density cathode generally uses Si-C composite material.
Summary of the invention
The disclosure passes through the solution that will be dissolved with element silicon, the solution dissolved with titanium elements and dissolved with the molten of carbon matrix precursor The multiple of liquid alternately mixes, and constructs the alternate composite construction of multilayer of oxide containing silicon and carbon simple substance, the multi-level body that silicon is isolated Product expansion and contraction, to reduce the pulverizing problem of silica-base material, and provide higher gram of specific capacity.
The technical problem that the present invention solves is to provide a kind of novel silicon-carbon core-shell material.
In some respects, a kind of core-shell material is provided, comprising:
Core, core contain Si oxide and titanium oxide；
First layer shell, first layer shell coat core；With
Second layer shell, second layer shell coat first layer shell.
In some embodiments, first layer shell contains one or more of material: carbon simple substance, Si oxide or titanyl Compound.
In some embodiments, second layer shell contains one or more of material: carbon simple substance, Si oxide or titanyl Compound.
In some embodiments, the first layer shell contains carbon simple substance.
In some embodiments, the second layer shell contains Si oxide and titanium oxide.
In some embodiments, 3~n-layer shell is also wrapped on except second layer shell, n is just whole more than or equal to 3 Number.
In some embodiments, each layer of shell contains one or more of each independently in 3~n-layer shell Material: carbon simple substance, Si oxide or titanium oxide.
In some embodiments, in 3~n-layer shell, the ingredient of adjacent two layers shell is identical or different, n >=4.
In some embodiments, core-shell material further includes item 1 below), 1)~2), 1)~3), 1)~4), 1)~ 5), 1)~6), 1)~7) or 1)~8): wherein
Third layer shell, the third layer shell coat the second layer shell, and the third layer shell contains carbon simple substance；
4th layer of shell, the 4th layer of shell coat the third layer shell, and the 4th layer of shell contains Si oxide and titanyl Compound；
Layer 5 shell, the layer 5 shell coat the 4th layer of shell, and five layers of shell contains carbon simple substance；
Layer 6 shell, the layer 6 shell coat the layer 5 shell, and the layer 6 shell contains Si oxide and titanyl Compound；
Layer 7 shell, the layer 7 shell coat the layer 6 shell, and seven layers of shell contains carbon simple substance；
8th layer of shell, the 8th layer of shell coat the layer 7 shell, and the 8th layer of shell contains Si oxide and titanyl Compound；
9th layer of shell, the 9th layer of shell coat the 8th layer of shell, and nine layers of shell contains carbon simple substance；
Tenth layer of shell, the described ten layer of shell coat the 9th layer of shell, and the described ten layer of shell contains Si oxide and titanyl Compound.
In some embodiments, Si oxide SiOx, 0.1 < x < 1.8.Such as 0.7≤x≤0.8.
In some embodiments, titanium oxide TiO2。
In some embodiments, each layer shell with a thickness of 5-200nm.
In some embodiments, the size (such as circumscribed circular diameter) of core is 20-300nm.
In some embodiments, the content of element silicon is 10wt% or more, such as 15wt% or more in core-shell material.
In some respects, the purposes that above-mentioned core-shell material is used as lithium ion battery anode active material is provided.
In some respects, a kind of battery is provided, above-mentioned core-shell material is contained.
In some respects, a kind of battery pack, including multiple batteries are provided, battery is the battery of any of the above-described.
In some respects, a kind of electric vehicle, including above-mentioned battery or above-mentioned battery pack are provided.
In some respects, a kind of electric appliance, including above-mentioned battery or above-mentioned battery pack are provided.
In some respects, a kind of method preparing core-shell material is provided, comprising the following steps:
(i) mixing carries out precipitation process, then dries, obtain containing silicon oxygen containing element silicon and containing the solution of titanium elements The mixture of compound and titanium oxide；
(ii) mixture containing Si oxide and titanium oxide is coated；
(iii) product of step ii) is coated.
In some embodiments, in step i), the precipitation process instigates element silicon and titanium elements in precipitating reagent The lower precipitating of effect.
In some embodiments, step ii) in, the cladding refers to the mixing containing Si oxide and titanium oxide Object is mixed with the solution dissolved with carbon matrix precursor, carries out drying and processing to mixture.
In some embodiments, step iii) in, the cladding refers to by the product of step ii) and dissolved with element silicon Solution and solution mixing dissolved with titanium elements, precipitate element silicon and titanium elements, collect sediment.
In some embodiments, the content of element silicon is 1~20wt% in the solution dissolved with element silicon.
In some embodiments, the content of titanium elements is 1~20wt% in the solution dissolved with titanium elements.
In some respects, a kind of method preparing core-shell material is provided, comprising the following steps:
A) it obtains the solution for being dissolved with element silicon, solution dissolved with titanium elements and is dissolved with carbon matrix precursor solution；
B) mixed dissolution has the solution of element silicon and the solution dissolved with titanium elements, precipitates element silicon and titanium elements, receives Collect sediment and carry out drying and processing, obtains core product；
C1 core product is mixed with the solution dissolved with carbon matrix precursor), drying and processing is carried out to mixture, obtains one layer of packet Cover product；
C2 product) is coated by one layer to mix with the solution dissolved with element silicon and the solution dissolved with titanium elements, keeps silicon first Element and titanium elements precipitating, collect sediment and carry out drying and processing, obtain two layers of cladding product；
D) in reducing atmosphere, previous step product is heat-treated.
In some embodiments, in step b), element silicon and titanium elements precipitate under the action of precipitating reagent.
In some embodiments, step c2) in, element silicon and titanium elements precipitate under the action of precipitating reagent.
In some embodiments, in step d), heat treatment temperature is 200-600 DEG C.
In some embodiments, in step d), heat treatment time 1-8h.
In some embodiments, in step b), element silicon and titanium elements precipitate under the action of precipitating reagent；
In some embodiments, step c2) in, element silicon and titanium elements precipitate under the action of precipitating reagent.
In some embodiments, in step d), heat treatment temperature is 200-600 DEG C；
In some embodiments, in step d), heat treatment time 1-8h.
In some embodiments, step c2) and d) between, further include any group of step c3 below), c3)~c4), C3)~c5), c3)~c6), c3) and~c7), c3) and c8), c3) and~c9) or c3)~c10)；Wherein
C3 product) is coated by two layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, is obtained Three layers of cladding product；
C4 product) is coated by three layers to mix with the solution dissolved with element silicon and the solution dissolved with titanium elements, keeps silicon first Element and titanium elements precipitate under the action of precipitating reagent, collect sediment and carry out drying and processing, obtain four layers of cladding product；
C5 product) is coated by four layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, is obtained Five layers of cladding product.
C6 product) is coated by five layers to mix with the solution dissolved with element silicon and the solution dissolved with titanium elements, keeps silicon first Element and titanium elements precipitate under the action of precipitating reagent, collect sediment and carry out drying and processing, obtain six layers of cladding product；
C7 product) is coated by six layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, is obtained Seven layers of cladding product.
C8 product) is coated by seven layers to mix with the solution dissolved with element silicon and the solution dissolved with titanium elements, keeps silicon first Element and titanium elements precipitate under the action of precipitating reagent, collect sediment and carry out drying and processing, obtain eight layers of cladding product；
C9 product) is coated by eight layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, is obtained Nine layers of cladding product；
C10 product) is coated by nine layers to mix with the solution dissolved with element silicon and the solution dissolved with titanium elements, keeps silicon first Element and titanium elements precipitate under the action of precipitating reagent, form the tenth layer of cladding product；
C11 product) is coated by ten layers to mix with the solution dissolved with element silicon and the solution dissolved with titanium elements, keeps silicon first Element and titanium elements precipitate under the action of precipitating reagent, form eleventh floor and coat product.
In some embodiments, the content of element silicon is 1~20wt% in the solution dissolved with element silicon；
In some embodiments, the content of titanium elements is 1~20% in the solution dissolved with titanium elements；
In some embodiments, the content dissolved with carbon in carbon matrix precursor solution is 30~80wt%；
In some embodiments, carbon matrix precursor solution organic matter is selected from glucose, chitosan, sucrose, citric acid, phenolic aldehyde One of resin is a variety of；
In some embodiments, precipitating reagent is selected from KOH, LiOH, NaOH, NH3.H2O、Na2CO3、K2CO3、Li2CO3In It is one or more；
In some embodiments, step c1), c3), c5), c7), c9) and/or c11) in, the temperature of drying and processing is 70-200℃；
In some embodiments, step c1), c3), c5), c7), c9) and/or c11) in, the time of drying and processing is 0.5-5h；
In some embodiments, step b), c2), c4), c6), c8) and/or c10) in, the temperature of drying and processing is 100-300℃；
In some embodiments, step b), c2), c4), c6), c8) and/or c10) in, the time of drying and processing is 0.5-5h；
In some embodiments, in step d), the temperature of heat treatment is 200-600 DEG C；
In some embodiments, in step d), the time of heat treatment is 1-8h；
In some embodiments, in step d), reducing atmosphere H2Or H2With N2Mixed gas (N2Volume ratio It is chosen as 10%-40%), H2- Ar mixed gas (Ar volume ratio is chosen as 10%-40%)；
In some embodiments, in step d), the flow velocity of gas is 1-10L/min under reducing atmosphere；
In some embodiments, the solution dissolved with element silicon is prepared as follows acquisition: silicon-containing material is dissolved Into liquid, wherein silicon-containing material is selected from silane, SiO2With one of Si simple substance or a variety of, liquid be selected from water, KOH solution, One of LiOH solution, NaOH solution and HF solution are a variety of；
In some embodiments, the solution dissolved with element silicon is prepared as follows acquisition: titaniferous materials are dissolved Into liquid, wherein titaniferous materials are selected from butyl titanate, tetraethyl titanate, isopropyl titanate and titanium tetrachloride and sulfuric acid oxygen Change one of titanium or a variety of, liquid is selected from one of water, ethyl alcohol, methanol, propyl alcohol, butanediol, glycerine, hydrochloric acid and sulfuric acid The more it plants；
In some embodiments, it is prepared dissolved with carbon matrix precursor solution by following method: carbon matrix precursor is molten Liquid organic matter is dissolved into liquid, and carbon matrix precursor solution organic matter is selected from glucose, chitosan, sucrose, citric acid, phenolic resin One of or it is a variety of, liquid be selected from one of water, ethyl alcohol, methanol, propyl alcohol, butanediol, glycerine or a variety of.
In some embodiments, the product of the disclosure can be obtained by disclosed method.
In some embodiments, disclosed method can obtain the product of the disclosure.
In some embodiments, the battery core shell of battery is hard shell or soft bag.
In some embodiments, the battery core shell of battery is soft bag, at this point, battery is soft-package battery.
In some embodiments, battery is lithium ion secondary battery.
In some respects, a kind of battery pack, including multiple above-mentioned batteries are provided.Optionally, in battery pack, multiple batteries that It is electrically connected between this.
In some respects, a kind of electric vehicle, including above-mentioned battery or battery pack are provided.
In some respects, a kind of electric appliance, including above-mentioned battery or battery pack are provided.
Term is explained:
" electric appliance " refers to all consuming devices, can be household electrical appliance, commercial appliance, industrial electric apparatus etc..
" electric vehicle " refers to all electrically driven (operated) vehicles, had both included the pure electric vehicle vehicles, and had also included Hybrid vehicles, wherein the vehicles may include vehicle, ship, aircraft etc..
Beneficial effect
Disclosure core-shell material can be used as lithium ion battery negative material, have the advantages that in one or more It is a:
Disclosure core-shell material uses SiOx-TiO2The alternate nano composite structure of the multilayer of mixture and carbon, at many levels every Volume expansion and contraction from silicon guarantee the integrality of silicon based anode material to reduce the pulverizing problem of silica-base material, improve The stability of lithium ion battery containing silicon based anode material.
The TiO that disclosure core-shell material contains2And carbon component, be conducive to the conduction of the electronics of the diffusion of lithium ion, thus Be conducive to the performance of material high rate performance.
Compared with the conventional silica-base material single in Graphite Coating, the ratio of silicon substantially increases disclosure core-shell material Add, gram specific capacity of material is also significant simultaneously to be increased, and 1000mAh/g or more is such as reached；
Disclosure core-shell material can guarantee the stability of material；
Disclosure core-shell material contains the silicon oxide sio of non-stoichiometricx(0.1 < x < 1.8), this is conducive to silicon substrate The stability of material.
Disclosure core-shell material is also mixed with TiO in containing2, this makes material have excellent lithium ion diffusivity, There is facilitation to the high rate performance of silicon based anode material；
Disclosure core-shell material is also mixed with TiO in containing2, can be relieved the volume change of silica-base material, be also beneficial to material The stability of material.
The ratio of silicon materials significantly improves in disclosure multi-layer core-shell material, and gram specific capacity of material is also mentioned significantly Rise, the stability of material also guaranteed, this in terms of high gram specific capacity cathode using being of great significance.
It is described in detail below in conjunction with embodiment of the drawings and examples to the disclosure, still, art technology Personnel will be understood that, following drawings and embodiment are merely to illustrate the disclosure, rather than the restriction to the scope of the present disclosure.According to attached The following detailed description of figure and preferred embodiment, the various purposes of the disclosure and advantageous aspect carry out those skilled in the art Saying will be apparent.
Detailed description of the invention
Fig. 1 is the partial schematic diagram of the core-shell material of one embodiment.
Specific embodiment
It is described in detail below in conjunction with embodiment of the embodiment to the disclosure, but those skilled in the art will Understand, the following example is merely to illustrate the disclosure, and should not be regarded as limiting the scope of the present disclosure.It is not specified in embodiment specific Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is It can be with conventional products that are commercially available.
It is referred to attached drawing below and word content understands between content of this disclosure and the disclosure and the prior art Distinctive points.Hereafter attached drawing and by way of enumerating some alternative embodiments of the disclosure, to the technical solution of the disclosure (including optimal technical scheme) is described in further detail.
It should be understood that any technical characteristic, any technical solution in the present embodiment are the technologies of plurality of optional One or more of feature or optional technical solution, in order to describe succinct to need the disclosure impossible to exhaust in this document All alternative technical characteristics and alternative technical solution, the embodiment for being also not easy to each technical characteristic are emphasized It is one of optional numerous embodiments, so those skilled in the art will appreciate that any that the disclosure can be provided Any two or more technical means or technical features that technological means is replaced or provides the disclosure carry out mutually group It closes and obtains new technical solution.
Embodiment 1
I. the solution for being dissolved with element silicon, the solution dissolved with titanium elements and the solution dissolved with carbon matrix precursor are obtained:
The silicon 50g (1.78mol) of simple substance is dissolved into the HF solution that 800g concentration is 10% mass percent, is occurred as follows Reaction: Si+4HF=SiF4+2H2, the solution 843g for being dissolved with element silicon is obtained, wherein the molar content of element silicon is 2.1mol.
The sulfuric acid oxidation titanium (3.2mol, CAS13825-74-6) of 500g is dissolved into the dilute sulfuric acid of the 0.1mol/L of 4500g In solution, the solution 5000g for being dissolved with titanium elements is obtained, wherein the molar content of titanium elements is 0.64mol.
100g glucose is dissolved into the water of 400g, obtains and is dissolved with carbon matrix precursor solution 500g, wherein glucose Mass content is 20%, and the mass percentage for being scaled carbon is 8%.
II. the solution by 100g dissolved with element silicon (containing element silicon 0.21mol) is dissolved with the solution of titanium elements with 500g (containing titanium elements 0.32mol) mixing obtains the solution dissolved with element silicon and titanium elements (Si:Ti molar ratio is 2:3).Stir shape Under state, Na is added dropwise in Xiang Shangshu solution2CO3Solution (concentration 0.3mol/L, volume 2L) is used as precipitating reagent.At this point, molten SiO is generated in liquid2Precipitating and TiO (OH)2Precipitating, the chemical reaction of generation have: SiF4+2Na2CO3+H2O=SiO2+4NaF+ 2H2CO3, TiOSO4+2H2O=TiO (OH)2+H2SO4, H2SO4+Na2CO3=Na2SO4+H2CO3.Collect sediment, i.e. SiO2With TiO(OH)2Mixture.The above sediment, drying and processing 2h, acquisition are produced in the core of dry state under 150 DEG C of air atmospheres Object.The ingredient of core product is SiO2-TiO2Mixture, quality 36g.
The glucose solution 27g that previous step product and concentration are 20wt% (is equivalent to 5.4g containing glucose, phase by III-1 It is mixed when in carbon elements 2.16g).It is evaporated liquid, and drying and processing 1h, acquisition under 100 DEG C of air atmospheres by residual solid The product coated by carbon precursor.
Previous step product is added to the solution dissolved with element silicon and titanium elements by III-2, and (ingredient is stirred in step II) It mixes under state, Na is added dropwise in Xiang Shangshu solution2CO3Solution (ingredient is used as precipitating reagent with step II), collects sediment, Drying and processing 2h under 150 DEG C of air atmospheres obtains the product in dry state, i.e., by SiO2-TiO2The product of mixture cladding.
The glucose solution 27g that previous step product and concentration are 20wt% (is equivalent to 5.4g containing glucose, phase by III-3 It is mixed when in carbon elements 2.16g).It is evaporated liquid, and drying and processing 1h, acquisition under 100 DEG C of air atmospheres by residual solid The product coated by carbon precursor.
III-4 to III-11: step III-2)~III-3) is repeated 4 times, is obtained product (+10 layers of shell of core)；
IV. previous step product is heat-treated in reducibility gas atmosphere, reducibility gas H2-N2Mixed gas (N2Body Product ratio is that 30%), reducibility gas flow velocity is 5L/min, and heat treatment temperature is 400 DEG C, heat treatment time 5h, is obtained real Apply the core-shell material of example 1.During drying and processing, SiO2Partial reduction occurs, forms SiO0.8；In addition, heat occurs for carbon matrix precursor Solution forms carbon simple substance.
Based on the above method, embodiment 1 obtains the structure of+10 layers of shell of core.Wherein, core, the second layer, the 4th layer, the 6th Layer, the 8th layer and the tenth layer ingredient be mainly SiO0.8With TiO2Mixture；First layer, third layer, layer 5, layer 7, 9th layer of ingredient is mainly carbon simple substance.
Embodiment 1 obtain core-shell material part as shown in Figure 1, as shown in the figure core 10 coated by first layer 21, first Layer 21 is coated by the second layer 22, and the second layer 22 is coated by third layer 23.For sake of brevity, do not show for the 4th layer to the tenth layer Out.
In the core-shell material that embodiment 1 obtains, the mass ratio of silicon is significantly improved, specifically ... internal layer SiO2-TiO2Mixing The quality of object is 36g, and Si:Ti molar ratio is 2:3, can calculate SiO2For 12g, TiO2For 24g.Outer layer (first layer) carbon coated Quality be 2.16g.The silicon-carbon and titanium oxygen compound of outside and the ratio of carbon are identical as internal layer and first layer, therefore, internal layer and The ratio of the silicon of first layer cladding is the ratio of the silicon of entire multilayer coating structure material.Internal layer SiO2Become after partial reduction SiO0.8, quality becomes 8.6g, siliceous 5.6g, and therefore, the ratio of silicon is 16%.
Embodiment 2
I. the solution for being dissolved with element silicon, the solution dissolved with titanium elements and the solution dissolved with carbon matrix precursor are obtained:
By silica 1 20g (2mol), it is dissolved into the KOH solution 1260g (252gKOH that concentration is 20% mass percent It is dissolved into 1008g water) (having 4.5mol KOH), following reaction: SiO occurs2+ 2KOH=K2SiO3+H2O is obtained and is dissolved with silicon The solution 1380g of the element, (SiO containing silicon source2) mass ratio be 8.7%.
By 570gTiCl4(3mol) is dissolved into 2.5% hydrochloric acid solution 5953g (hydrochloric 4.1mol), obtains titaniferous Source (TiCl4) mass ratio be 8.7% hydrochloric acid solution 6523g.
By citric acid (C6H8O7.H2O) 630g (3mol), is dissolved into the water of 864g, obtains (the C containing citric acid6H8O7) 40% aqueous solution 1494g.
II. the solution (siliceous 0.2mol) by 138g dissolved with element silicon (contains with 652.3g dissolved with the solution of titanium elements Titanium 0.3mol) it is slowly mixed together, when mixing, persistently stirs.During mixing, there is sediment generation.The chemical reaction of generation Have: KOH+HCl=KCl+H2O, K2SiO3+ 2HCl=H2SiO3(precipitating)+2KCl, TiCl4+3H2O=TiO (OH)2(precipitating)+ 4HCl.Sediment is SiO2-TiO(OH)2Mixture.Sediment, drying and processing 2h, acquisition are in dry under 160 DEG C of air atmospheres The core product of dry state, core product component are SiO2-TiO2, quality 31g.
III-1. it takes 40% citric acid solution 17g to mix with previous step product, is evaporated liquid, and residual solid is existed Drying and processing 1h under 130 DEG C of air atmospheres obtains the product coated by carbon precursor.
III-2. the solution containing the solution for being dissolved with element silicon and dissolved with titanium elements is alternately added previous step on a small quantity It in product, is stirred continuously simultaneously, after the sediment washing of acquisition, the drying and processing 2h under 160 DEG C of air atmospheres obtains quilt SiO2-TiO2The product of mixture cladding.
III-3. it takes 40% citric acid solution 17g to mix with previous step product, is evaporated liquid, and residual solid is existed Drying and processing 1h under 130 DEG C of air atmospheres obtains the product coated by carbon precursor.
III-4 to III-9: step III-2)~III-3) is repeated 3 times, is obtained product (+8 layers of shell of core)；
IV. in H2-N2Mixed gas (N2Volume ratio is 15%) to be heat-treated in atmosphere to previous step product, gas Flow velocity is 5L/min, and heat treatment temperature is 400 DEG C, heat treatment time 5h.Make SiO2Partial reduction occurs, forms SiO0.7.Separately Outside, carbon matrix precursor occurs pyrolysis and forms carbon simple substance.
Based on the above method, embodiment 1 obtains the structure of+8 layers of shell of core.Wherein, core, the second layer, the 4th layer, layer 6 Ingredient with the 8th layer is mainly SiO0.7With TiO2Mixture；First layer, third layer, layer 5 and layer 7 ingredient master It to be carbon simple substance.
Inventor it is known that the ratio of traditional silicon admixed graphite less than 10%, generally 5% or so.It is carried out in graphite surface The silica-base material of nanometer is coated, ratio is also universal relatively low, and generally less than 5%.
However, the mass ratio of silicon significantly improves in the core-shell material that embodiment 2 obtains, and specifically, the SiO of internal layer2- TiO2Quality be 31g, by mixed liquor design Si/Ti molar ratio 2:3 based on, contain SiO210.3g (i.e. 0.17mol, it is siliceous 4.76g), TiO220.7g.After finally carrying out reductive heat treatment, SiO2It is transformed into SiO0.7, quality becomes 5.0g.Carbon coating Quality is 2.48g, then the mass ratio of silicon is 16.9%.Because the subsequent cladding that repeats is to carry out in the same proportion, finally obtain Multi-level covering material, the mass ratio of silicon is also 16.9%.
The multilevel-coated material that this patent is developed, the ratio of silicon materials significantly improve, and gram specific capacity of material also obtains To greatly promoting, the stability of material is also guaranteed, this application in terms of high gram specific capacity cathode is of great significance.
Any technical solution disclosed in the above-mentioned disclosure unless otherwise stated, if it discloses numberical range, Disclosed numberical range is preferred numberical range, and any it should be appreciated by those skilled in the art preferred numberical ranges The only obvious or representative numerical value of technical effect in many enforceable numerical value.It, can not since numerical value is more Exhaustion, so the disclosure discloses component values just to illustrate the technical solution of the disclosure, also, the above-mentioned numerical value enumerated is not The limitation that protection scope is created to the disclosure should be constituted.
In addition, for indicating the art of positional relationship or shape applied in any technical solution disclosed in the above-mentioned disclosure Its meaning includes approximate with its, similar or close state or shape to language unless otherwise stated.The either component that the disclosure provides Either being assembled by multiple individual component parts, or the separate part that integrally formed technique manufactures.
Finally it should be noted that: above embodiments are only to illustrate the technical solution of the disclosure rather than its limitations；To the greatest extent Pipe is described in detail the disclosure referring to preferred embodiment, it should be understood by those ordinary skilled in the art that: still It can modify to the specific embodiment of the disclosure or some technical features can be equivalently replaced；Without departing from this public affairs The spirit of technical solution is opened, should all be covered in the claimed technical proposal scope of the disclosure.

Claims (20)

1. a kind of core-shell material, comprising:
Core, the core contain Si oxide and titanium oxide；
First layer shell, the first layer shell coat the core；With
Second layer shell, the second layer shell coat the first layer shell.
2. core-shell material according to claim 1, it is characterised in that following one or more:
The first layer shell contains carbon simple substance；
The second layer shell contains Si oxide and titanium oxide.
3. core-shell material according to claim 1, be also wrapped on 3~n-layer shell except the second layer shell, n be greater than Or the positive integer equal to 3.
4. core-shell material according to claim 3, each layer of shell contains following each independently in 3~n-layer shell One or more materials: carbon simple substance, Si oxide or titanium oxide.
5. core-shell material according to claim 3, in 3~n-layer shell, the ingredient of adjacent two layers shell is identical or not Together, n >=4.
6. core-shell material according to claim 1 further includes item 1 below), 1)~2), 1)~3), 1)~4), 1)~ 5), 1)~6), 1)~7) or 1)~8): wherein
1) third layer shell, the third layer shell coat the second layer shell, and the third layer shell contains carbon simple substance；
2) the 4th layer of shell, the 4th layer of shell coat the third layer shell, and the 4th layer of shell contains Si oxide and titanyl Object；
3) layer 5 shell, the layer 5 shell coat the 4th layer of shell, and five layers of shell contains carbon simple substance；
4) layer 6 shell, the layer 6 shell coat the layer 5 shell, and the layer 6 shell contains Si oxide and titanyl Object；
5) layer 7 shell, the layer 7 shell coat the layer 6 shell, and seven layers of shell contains carbon simple substance；
6) the 8th layer of shell, the 8th layer of shell coat the layer 7 shell, and the 8th layer of shell contains Si oxide and titanyl Object；
7) the 9th layer of shell, the 9th layer of shell coat the 8th layer of shell, and nine layers of shell contains carbon simple substance；
8) the tenth layer of shell, the described ten layer of shell coat the 9th layer of shell, and the described ten layer of shell contains Si oxide and titanyl Object.
7. described in any item core-shell materials according to claim 1~6, it is characterised in that following one or more:
The Si oxide is SiOx, 0.1 < x < 1.8；
The titanium oxide is TiO2；
Each layer shell with a thickness of 5-200nm；
The content of element silicon is 10wt% or more, such as 15wt% or more in the core-shell material.
8. the purposes that the described in any item core-shell materials of claim 1~7 are used as lithium ion battery anode active material.
9. a kind of battery contains the described in any item core-shell materials of claim 1~7.
10. a kind of battery pack, which is characterized in that including multiple batteries, the battery is battery as claimed in claim 9.
11. a kind of electric vehicle, which is characterized in that including battery as claimed in claim 9 or described in any one of claim 10 Battery pack.
12. a kind of electric appliance, which is characterized in that including battery as claimed in claim 9 or battery pack described in any one of claim 10.
13. a kind of method for preparing core-shell material, comprising the following steps:
(i) mixed dissolution has the solution of element silicon and the solution dissolved with titanium elements, carries out precipitation process, then dries, obtain Mixture containing Si oxide and titanium oxide；
(ii) mixture containing Si oxide and titanium oxide is coated；
(iii) product of step ii) is coated again.
14. preparing the method for core-shell material according to power 13, it is characterised in that it is following one or more,
In step i), the precipitation process is that element silicon and titanium elements is instigated to precipitate under the action of precipitating reagent；
Step ii) in, the cladding refers to the mixture containing Si oxide and titanium oxide and is dissolved with carbon matrix precursor Solution mixing carries out drying and processing to mixture；
Step iii) in, the cladding refers to the product of step ii) with the solution dissolved with element silicon and dissolved with titanium elements Solution mixing, precipitate element silicon and titanium elements, collect sediment.
15. preparing the method for core-shell material according to power 13 or 14, it is characterised in that it is following one or more,
The content of element silicon is 1~20wt% in solution dissolved with element silicon；
The content of titanium elements is 1~20wt% in solution dissolved with titanium elements；
Content dissolved with carbon in carbon matrix precursor solution is 30~80wt%.
16. a kind of method for preparing core-shell material, comprising the following steps:
A) it obtains the solution for being dissolved with element silicon, solution dissolved with titanium elements and is dissolved with carbon matrix precursor solution；
B) mixed dissolution has the solution of element silicon and the solution dissolved with titanium elements, precipitates element silicon and titanium elements, and it is heavy to collect Starch carries out drying and processing, obtains core product；
C1 core product is mixed with the solution dissolved with carbon matrix precursor), drying and processing is carried out to mixture, one layer of cladding is obtained and produces Object；
C2) product is coated by one layer to mix with the solution dissolved with element silicon with solution dissolved with titanium elements, make element silicon with Titanium elements precipitating collects sediment and carries out drying and processing, obtains two layers of cladding product；
D) in reducing atmosphere, previous step product is heat-treated.
17. according to the method for claim 16, it is characterised in that following one or more:
In step b), element silicon and titanium elements precipitate under the action of precipitating reagent；
Step c2) in, element silicon and titanium elements precipitate under the action of precipitating reagent；
In step d), heat treatment temperature is 200-600 DEG C；
In step d), heat treatment time 1-8h.
18. according to the method for claim 16, step c2) and d) between, further include any group of step c3 below), c3) ~c4), c3)~c5), c3) and~c6), c3) and~c7), c3) and c8), c3) and~c9) or c3)~c10)；Wherein
C3 product) is coated by two layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, obtains three layers Coat product；
C4) products are coated by three layers to mix with the solution dissolved with element silicon with solution dissolved with titanium elements, make element silicon with Titanium elements precipitate under the action of precipitating reagent, collect sediment and carry out drying and processing, obtain four layers of cladding product；
C5 product) is coated by four layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, obtains five layers Coat product；
C6) products are coated by five layers to mix with the solution dissolved with element silicon with solution dissolved with titanium elements, make element silicon with Titanium elements precipitate under the action of precipitating reagent, collect sediment and carry out drying and processing, obtain six layers of cladding product；
C7 product) is coated by six layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, obtains seven layers Coat product；
C8) products are coated by seven layers to mix with the solution dissolved with element silicon with solution dissolved with titanium elements, make element silicon with Titanium elements precipitate under the action of precipitating reagent, collect sediment and carry out drying and processing, obtain eight layers of cladding product；
C9 product) is coated by eight layers to mix with the solution dissolved with carbon matrix precursor, and drying and processing is carried out to mixture, obtains nine layers Coat product；
C10) products are coated by nine layers to mix with the solution dissolved with element silicon with solution dissolved with titanium elements, make element silicon with Titanium elements precipitate under the action of precipitating reagent, form the tenth layer of cladding product；
C11) products are coated by ten layers to mix with the solution dissolved with element silicon with solution dissolved with titanium elements, make element silicon with Titanium elements precipitate under the action of precipitating reagent, form eleventh floor and coat product.
19. according to the method for claim 16, it is characterised in that one or more:
The content of element silicon is 1~20wt% in solution dissolved with element silicon；
The content of titanium elements is 1~20% in solution dissolved with titanium elements；
Content dissolved with carbon in carbon matrix precursor solution is 30~80wt%.
20. 3~19 described in any item methods according to claim 1, it is characterised in that one or more:
The carbon matrix precursor solution organic matter is selected from one of glucose, chitosan, sucrose, citric acid, phenolic resin or more Kind；
The precipitating reagent is selected from KOH, LiOH, NaOH, NH3.H2O、Na2CO3、K2CO3、Li2CO3One of or it is a variety of；
Step c1), c3), c5), c7), c9) and/or c11) in, the temperature of drying and processing is 70-200 DEG C；
Step c1), c3), c5), c7), c9) and/or c11) in, time of drying and processing is 0.5-5h；
Step b), c2), c4), c6), c8) and/or c10) in, the temperature of drying and processing is 100-300 DEG C；
Step b), c2), c4), c6), c8) and/or c10) in, time of drying and processing is 0.5-5h；
Reducing atmosphere is H2Or H2With N2Mixed gas (N2Volume ratio is chosen as 10%-40%), H2- Ar mixed gas (Ar volume ratio is chosen as 10%-40%)；
The flow velocity of gas is 1-10L/min under reducing atmosphere；
Solution dissolved with element silicon is prepared as follows acquisition: silicon-containing material being dissolved into liquid, wherein described to contain Silicon matter is selected from silane, SiO2With one of Si simple substance or a variety of, the liquid be selected from water, KOH solution, LiOH solution, One of NaOH solution and HF solution are a variety of；
Solution dissolved with element silicon is prepared as follows acquisition: titaniferous materials being dissolved into liquid, wherein described to contain Titanium substance is selected from one of butyl titanate, tetraethyl titanate, isopropyl titanate and titanium tetrachloride and sulfuric acid oxidation titanium or more Kind, the liquid is selected from one of water, ethyl alcohol, methanol, propyl alcohol, butanediol, glycerine, hydrochloric acid and sulfuric acid and the more plants；
It is prepared dissolved with carbon matrix precursor solution by following method: carbon matrix precursor solution organic matter is dissolved into liquid, The carbon matrix precursor solution organic matter is selected from one of glucose, chitosan, sucrose, citric acid, phenolic resin or a variety of, institute It states liquid and is selected from one of water, ethyl alcohol, methanol, propyl alcohol, butanediol, glycerine or a variety of.
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