WO2020103914A1 - 一种硅氧复合负极材料及其制作方法 - Google Patents

一种硅氧复合负极材料及其制作方法

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Publication number
WO2020103914A1
WO2020103914A1 PCT/CN2019/120043 CN2019120043W WO2020103914A1 WO 2020103914 A1 WO2020103914 A1 WO 2020103914A1 CN 2019120043 W CN2019120043 W CN 2019120043W WO 2020103914 A1 WO2020103914 A1 WO 2020103914A1
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Prior art keywords
lithium
silicon
inner core
intermediate layer
silicon oxide
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PCT/CN2019/120043
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English (en)
French (fr)
Inventor
沙玉静
夏圣安
王平华
Original Assignee
华为技术有限公司
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Publication date
Priority claimed from CN201811481527.5A external-priority patent/CN109755500B/zh
Application filed by 华为技术有限公司 filed Critical 华为技术有限公司
Priority to EP19888193.0A priority Critical patent/EP3879605A4/en
Publication of WO2020103914A1 publication Critical patent/WO2020103914A1/zh
Priority to US17/325,302 priority patent/US20210288316A1/en

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/32—Alkali metal silicates
    • C01B33/325—After-treatment, e.g. purification or stabilisation of solutions, granulation; Dissolution; Obtaining solid silicate, e.g. from a solution by spray-drying, flashing off water or adding a coagulant
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/46—Accumulators structurally combined with charging apparatus
    • 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
    • H01M4/36—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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
    • H02J7/00—Circuit arrangements for charging or depolarising batteries or for supplying loads from batteries
    • H02J7/0068—Battery or charger load switching, e.g. concurrent charging and load supply
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

Definitions

  • the invention relates to the technical field of secondary batteries, in particular to a silicon-oxygen composite anode material and a manufacturing method thereof.
  • silicon oxide will form irreversible lithium oxide (Li 2 O) and lithium silicate (Li x Si y O z ) by-products during the insertion of lithium ions, which can serve as a natural buffer layer to relieve the silicon-lithium alloy Li x Si in
  • the volume expansion during lithium ion intercalation avoids problems such as particle breakage caused by excessive expansion of the silicon material, unstable SEI film on the surface of the material, continuous consumption of active Li ions in the electrolyte, and final cycle life decay too fast.
  • the battery cycle life and capacity retention rate of negative electrodes tend to be higher than ordinary silicon carbon materials.
  • the first effect of the traditional silicon oxide anode is less than 80%, and the first effect of the cathode material is generally greater than 85%.
  • the positive and negative electrode materials are matched, the lithium ions provided in the positive electrode material will be sacrificed to form an irreversible capacity at the negative electrode. Insufficient capacity play affects the overall battery capacity and energy density. Therefore, how to improve the first effect of the negative electrode material silicon oxide is an urgent problem to be solved.
  • the embodiments of the present invention provide a silicon-oxygen composite anode material and a manufacturing method thereof, which can effectively solve the problem of low first-effect of the existing silicon-oxygen composite anode material.
  • An embodiment of the present invention provides a silicon-oxygen composite negative electrode material for making a negative electrode of a lithium battery.
  • the negative electrode material includes a core, a coating layer wrapped around the core, and the core and the coating layer Intermediate layer, wherein the intermediate layer includes the non-lithium silicate, and the mass content of the non-lithium silicate in the intermediate layer is distributed from the intermediate layer to the inner core .
  • the decrement includes a gradient decrease from the intermediate layer to the core.
  • the gradient decrease refers to the same mass ratio on the circumference at the same distance from the center of the core, as the distance from the center of the core decreases The proportion of the mass decreases gradually.
  • the non-lithium silicate is generated in situ on the outer layer of the inner core, and has a dense structure of water-insoluble or non-alkaline or weakly alkaline, which can effectively relieve the dissolution of the internal water-soluble lithium silicate and reduce the ghost-eye complex
  • the pH value of the negative electrode material is generated in situ on the outer layer of the inner core, and has a dense structure of water-insoluble or non-alkaline or weakly alkaline, which can effectively relieve the dissolution of the internal water-soluble lithium silicate and reduce the ghost-eye complex.
  • the pH value of the composite anode material can be reduced, so that it can maintain better processing performance, and can simultaneously take into account the electrochemical performance and processing stability of the material.
  • the intermediate layer also includes silicon oxide, the chemical formula of which is SiO x , where 0.6 ⁇ x ⁇ 2, where x is an independent variable of the chemical formula SiO x , and the mass content distribution of the silicon oxide is opposite to that of the non-lithium silicate.
  • the inner core includes a mixture of nano-silicon, silicon oxide, and lithium silicate.
  • the mass distribution ratio of silicon oxide in the entire inner core is increased by a gradient along the cladding layer toward the inner core in a radial direction.
  • the mass content of the lithium silicate in the inner core is reduced by the gradient from the coating layer to the inner core.
  • the content of nano-silicon and silicate decreases from outside to inside, and the content of silicon oxide increases from outside to inside.
  • This gradient structure can prevent the doping reaction in the core of the material. Too much nano-silicon content can effectively reduce the stress that the core bears during the charging and discharging process, and avoid the core from breaking for a long time.
  • a plurality of holes are formed in the inner core and the intermediate layer, the holes extend from the surface of the intermediate layer from outside to inward, and the channels are tapered holes, and the pore diameter of the channels is from the surface of the intermediate layer to the The inner 1 center gradually shrinks.
  • the "trumpet" channel structure extending from the particle surface of the material to the inner core direction and not completely connected can effectively relieve the expansion of the outer layer of high-first-effect silicon oxide particles during charging and discharging; and there is no gap between the channel and the channel A complete communication structure is formed, which can prevent the structural collapse and performance degradation caused by excessive side reactions between the electrolyte and the material caused by too deep pores; in addition, the multi-lithium ion diffusion channel provided by the porous structure can improve the fast charging ability of the material .
  • the intermediate layer is a mixture layer formed by introducing a reaction of non-lithium metal salt on the surface of the inner core, and the non-lithium silicate is formed in situ on the surface of the inner core material, which can ensure the stability of the material structure and is not water-soluble / Non-alkaline / weakly alkaline compact structure can effectively ease the dissolution of internal water-soluble lithium silicate and lower the pH value of the material.
  • the coating layer is a carbonaceous material, the carbonaceous material is purely composed of amorphous carbon, or the carbonaceous material is composed of the amorphous carbon and the embedded carbon nanotubes or graphene mixture.
  • the coating layer includes an organic material polymerization or polymer dispersion coating to form a coating layer, and the coating layer has a thickness of 2 to 200 nm.
  • the carbonaceous coating layer or organic polymer coating layer can increase the electronic conductivity of the material, and at the same time the coating layer structure can prevent the electrolyte from directly contacting with the active material to generate excessive surface side reactions, reduce the irreversible capacity and lithium in the battery
  • the loss of ions in addition, the coating layer can play a certain role in inhibiting the expansion and contraction of the material during the charging and discharging process, and comprehensively play the role of improving the cycle performance of the battery.
  • FIG. 1 is a structural diagram of a battery using a silicon-oxygen composite anode material according to an embodiment of the present invention.
  • FIG. 2 is a schematic structural diagram of an oxygen composite anode material provided by the first embodiment of the present invention.
  • FIG. 3 is a mass concentration distribution diagram of a silicon-oxygen composite anode material component provided by the first embodiment of the present invention.
  • FIG. 4 is a cross-sectional electron micrograph of a sample of a silicon-oxygen composite anode material provided by the first embodiment of the present invention.
  • FIG. 5 is a schematic view of a porous structure of a silicon-oxygen composite anode material provided by a second embodiment of the present invention.
  • FIG. 6 is a manufacturing flowchart of a silicon-oxygen composite anode material provided by a method embodiment of the present invention.
  • FIG. 7 is a surface electron micrograph of a silicon-oxygen composite anode material provided by a second embodiment of the present invention.
  • the embodiment of the present invention mainly relates to a new silicon-oxygen composite negative electrode material, which is used to make a negative electrode of a lithium battery.
  • the lithium battery is mainly used in terminal consumer products, such as various mobile phones, tablet computers, notebook computers, and other wearable or removable electronic devices.
  • the core components of the lithium battery include a positive electrode material 101, a negative electrode material 102, an electrolyte 103, a separator 104, and corresponding communication accessories and circuits.
  • the positive and negative electrode materials can deintercalate lithium ions to achieve energy storage and release
  • the electrolyte is a carrier for lithium ions to be transferred between the positive and negative electrodes
  • the separator can permeate lithium ions but is not conductive to positive and negative
  • the poles are separated to prevent short circuits.
  • the positive composite negative electrode material usually plays a decisive role in the key performance factors such as the energy storage function of the lithium battery, the energy density of its cell, cycle performance and safety.
  • the negative electrode material of the embodiment of the present invention focuses on a silicon oxide composite negative electrode material with high specific capacity (mAh / g).
  • the lithium silicate salt formed by lithium doping changes the crystal structure of the material and reduces irreversible reactions, thereby enhancing its first effect on the basis of maintaining a higher specific gravity of the silicon oxide material and achieving the goal of increasing the energy density of the cell.
  • the pH value of the composite negative electrode material can be reduced, so that it can maintain better processing performance, and can simultaneously take into account the electrochemical performance and processing stability of the material.
  • the surface of the composite negative electrode material of the embodiment of the present invention has a radial tapered hole structure, which can relieve the volume expansion of the material during charging and discharging and provide a richer lithium ion transmission channel, which is conducive to the improvement of the long cycle life of the battery. The overall competitiveness of the product.
  • the silicon-oxygen composite anode material of the first embodiment of the present invention includes a core 1, a coating layer 3 coated on the outer surface of the core 1, and an intermediate layer 2 between the core 1 and the coating layer 3 .
  • the core 1 is a lithium-doped silicon oxide core, wherein the lithium-doped silicon oxide core is a mixture of multiple materials.
  • the inner core 1 includes a mixture of nano silicon (silicon), silicon oxide, and lithium silicate, wherein the particle radius r of the mixture is 50 nm to 20 um.
  • the silicon oxide of the chemical formula SiO x wherein 0.6 ⁇ x ⁇ 2, wherein the chemical formula SiO x x oriented independent variable, there is no relationship with the other chemical formulas x.
  • the subscript variables used in the following chemical formulas to express the molecular number ratio are also the same as the principle of x.
  • the same letters in different chemical formulas such as x, y, etc. are not related, but are not distinguished for convenience. .
  • the increment can be a gradient increase, for example, it can refer to the same mass ratio on the circumference with the same distance from the center of the silicon oxide anode material, which changes gradually or stepwise as the distance from the center of the anode material changes.
  • the chemical formula of the lithium silicate is Li 2x Si y O (x + 2y) , which is a product formed after the reaction of lithium-doped silicon oxide, and is a mixture of various silicates, and its composition includes but is not limited to Li 4 SiO 4 , Li 2 SiO 3 and Li 2 Si 2 O 5 etc.
  • the mass content distribution of the lithium silicate in the inner core 1 decreases from the cladding layer 3 to the inner core 1, that is, the outermost layer of the inner core 1 has the highest mass ratio of lithium silicate, and then Step by step toward the center of the core 1.
  • the inner core 1 and the intermediate layer 2 further include non-metallic doping elements such as C, H, N, B, P, S, Cl, and F, and the non-metallic doping elements have a gradient in the inner core 1 Distribution, the gradient distribution is decreasing from the outside of the middle layer 2 to the center of the core 1.
  • the non-metal elements such as C, H, N, B, P, S, Cl, and F exist in a doped form in any one or more compounds of the mixture of the inner core 1 and the intermediate layer 2, and the doped
  • the molar ratio of the hetero element to the doped substance is less than 5%.
  • the gradient distribution is based on the principle of diffusion.
  • the amount of lithium source added and the synthesis temperature are controlled.
  • the concentration of the lithium source in the material decreases from the outside to the inside as a gradient. Therefore, the nano-silicon and silicon in the core 1
  • the content of acid salt decreases from outside to inside, and the content of silicon oxide increases from outside to inside.
  • the core structure formed by the gradient distribution can prevent too much nano silicon content in the material core due to the doping reaction, and can effectively reduce the stress that the core bears during the charging and discharging process of the core, and prevent the core from breaking due to long-term cycling.
  • the lithium-doped component of the silicon-oxygen composite anode material is mainly contained in lithium silicate and nano-lithium, and the mass content in the inner core 1 is reduced by the gradient from the coating layer 3 to the inner core 1 That is, the outermost layer of the inner shell 1 has the highest mass ratio of doped lithium elements, and then decreases layer by layer toward the center of the inner core 1.
  • the intermediate layer 2 generates non-lithium silicate in situ on the surface of the inner core 1, that is, the intermediate layer 2 is a mixture layer formed by introducing a non-lithium metal salt on the surface of the inner core 1 and reacting.
  • the intermediate layer 2 includes non-lithium silicate, nano silicon, silicon oxide, and lithium silicate.
  • the non-lithium silicate refers to a doped metal silicate other than lithium silicate.
  • the chemical formula of the non-lithium silicate is M x Si y O z , wherein M includes one or more combinations of metal elements such as Al, Ca, Mg, Be, Sr, Ba, and Ti. As shown in FIG.
  • the mass content distribution of the non-lithium silicate in the intermediate layer 2 decreases from the cladding layer 3 to the inner core 1, which is the outermost layer of the intermediate layer 2 Of non-lithium silicates have the highest mass ratio, and the closer the non-lithium silicates to the center of the inner core 1 are, the lower the mass ratio of the entire intermediate layer 2 is.
  • the non-lithium silicate is generated in situ on the outer layer of the inner core 1 and has a dense structure that is not water-soluble or non-alkaline or weakly alkaline, which can effectively relieve the dissolution of the internal water-soluble lithium silicate and reduce the ghost eyes
  • the pH value of the composite anode material further includes silicon oxide, and its chemical formula is SiO x , where 0.6 ⁇ x ⁇ 2, where x is an independent variable of the chemical formula SiO x , and the mass distribution of silicon oxide is opposite to that of the non-lithium silicate.
  • the mass content distribution of the silicon oxide in the intermediate layer 2 is increased by the gradient of the cladding layer 3 toward the inner core 1, that is, the mass percentage of the non-lithium silicate of the outermost layer of the intermediate layer 2
  • the ratio is the least, and then the closer the mass ratio of non-lithium silicate to the center of the inner core 1 in the entire intermediate layer 2 is, the higher.
  • the intermediate layer also includes a mixture of nano-silicon, silicon oxide, and lithium silicate.
  • Fig. 4 shows the secondary electron image of the cut surface of the silicon-oxygen composite anode material sample and the distribution diagram of the element Mg (when M in M x Si y O z is Mg).
  • the cut surface view can observe the internal Structure distribution, of which Figure 4 is an electron microscope image using secondary electron imaging and double electron imaging, mainly used for surface micro-topography observation or surface element distribution observation.
  • the light gray part is the non-lithium silicate Mg2SiO4 formed in situ on the surface of part of the lithium-doped silicon oxide.
  • the right part of FIG. 4 corresponds to the distribution of the Mg element and the left part. The contours are consistent, and as can be seen from the right part, the Mg concentration is a gradient distribution that decreases from the outer layer to the inner core region.
  • the coating layer 3 is not an essential component of the silicon-oxygen composite anode material in the embodiments of the present invention. In some embodiments, the coating layer 3 may not be provided. In some embodiments, the coating layer 3 is a carbonaceous material, and a coating layer structure is formed on the outermost layer of the silicon-oxygen composite anode material, and the coating layer thickness may be 2 to 1000 nm.
  • the carbonaceous material is amorphous carbon formed by cracking a carbon source, or a mixture of amorphous carbon and carbon nanotubes embedded therein and / or graphene.
  • the coating layer 3 may be a carbonaceous material and / or organic polymer coating layer, the carbonaceous material coating layer can increase the electronic conductivity of the material, and the coating layer structure can prevent the electrolyte from directly contacting the active material Excessive surface side reactions occur, reducing irreversible capacity and loss of lithium ions in the battery.
  • the silicon-oxygen composite anode material in the second embodiment of the present invention has a porous structure on the inner core 1 and the intermediate layer 2.
  • a plurality of holes 12 are formed on the silicon-oxygen composite anode material, the holes 12 extend from the surface of the intermediate layer 2 from outside to inward, and the holes 12 are tapered holes, and the diameter of the holes 12 is from the middle
  • the surface of the layer 2 gradually decreases toward the center of the inner core 1, that is, the pore diameter decreases gradually along the direction from the surface of the intermediate layer 2 into the inner core 1.
  • the opening diameter of the pores 12 on the surface of the intermediate layer 2 is larger than the pore diameter of the portion of the core 1, that is, D out > D in , and the depth of the pores 12 is smaller than the particle radius r of the mixture of the core 1, That is, D depth ⁇ r, and 10nm ⁇ D depth ⁇ 500nm.
  • the openings of the channels 12 are evenly distributed on the surface of the intermediate layer 2, and each channel 12 extends along the surface of the intermediate layer 2 toward the center of the inner core 1 in the radial direction.
  • the structure characteristic of the gradient lithium-doped silicon oxide of the inner core 1 is that the doping concentration decreases from the surface to the axis of the particle, the distribution of nano-Si particles on the surface of the inner core 1 is the most, from the intermediate layer 2 and the surface of the inner core 1 to the axis
  • the direction-derived porous channel structure design can alleviate the expansion of the outer layer of high-efficiency silicon oxide particles during charging and discharging, and the channel 12 and the channel 12 do not form a complete communication structure, which can prevent the channel 12 from being too deep to cause electrolysis Structural collapse and performance degradation caused by excessive side reactions between the liquid and the material.
  • the porous channel structure provides more lithium ion diffusion channels, which can enhance the fast charging ability of the material.
  • the coating layer 3 includes a polymer coating layer formed by organic substance polymerization or polymer dispersion coating.
  • the polymer coating layer 3 not only covers the surface of the intermediate layer 2 but also completely fills all the pores 12 of the inner core 1 and the intermediate layer 2. In some embodiments, the cladding layer 3 only fills part of the holes 12.
  • the polymer coating layer 3 directly covers the surface of the inner core 1 and also completely fills all the channels 12 of the inner core 1. In some embodiments, the cladding layer 3 only fills a part of the channels 12.
  • a method embodiment of the present invention provides a method for manufacturing a silicon-oxygen composite anode material in the first embodiment.
  • the production method mainly includes the following steps:
  • Step 1 Preparation of partially lithium-doped silicon oxide: the silicon oxide and the lithium source are mixed evenly according to a certain ratio, and then transferred to a sagger, and baked in an inert atmosphere or a reducing atmosphere.
  • the silicon oxide and the lithium source are mixed uniformly according to a certain ratio, and then transferred to a sagger (0.1 ⁇ n Li / n Si ⁇ 1.0, where n Li / n Si is the molar ratio between lithium ions and silicon oxide ), And then transfer the sagger to a high-temperature furnace with an inert atmosphere or a reducing atmosphere, and perform a roasting reaction.
  • the roasting temperature is in the temperature range of 300 to 900 ° C, and partially lithium-doped silicon oxide, that is, lithium silicate Mixture with silicon oxide.
  • the lithium source used for the lithiated doping is a lithium salt, and the lithium salt mainly includes one or more of LiH, LiAlH 4 , Li 2 CO 3 , LiNO 3 , LiAc, and LiOH.
  • Step 2 In-situ synthesis of non-lithium silicate: the partially lithiated doped silicon oxide and non-lithium metal or metal salt are uniformly mixed at a certain ratio and then roasted.
  • the partially lithiated doped silicon oxide and non-lithium metal or metal salt are uniformly mixed at a certain ratio to obtain a mixture, and the mixture is transferred to a high-temperature furnace in an inert atmosphere or a reducing atmosphere in a sagger for 400-1000
  • the calcination in the temperature range of °C generates non-lithium silicate on the surface of partially lithium-doped silicon oxide or porous partially lithium-doped silicon oxide, resulting in a layered structure and gradient distribution of lithium-doped silicon oxide composite materials.
  • the layered structure refers to a structure in which the lithium-doped silicon oxide composite material includes the inner core 1 and the intermediate layer 2 in the foregoing embodiment.
  • the structural formula of the non-lithium silicate is M x Si y O z , M includes but is not limited to one or more metal elements such as Al, Ca, Mg, Be, Sr, Ba, Ti, Zr, etc. M also includes but It is not limited to the elemental metal or metal salt of the metal element, wherein the molar ratio of the metal element M to Si satisfies 0.01 ⁇ n M / n Si ⁇ 0.3.
  • Step 3 Secondary coating of carbonaceous material: the lithium-doped silicon oxide composite material synthesized in step 2 is placed in an inert atmosphere furnace, and an organic carbon source gas is introduced to cause a cracking reaction at a high temperature, so that A carbonaceous coating layer is formed on the surface of the lithium-doped silicon oxide composite material.
  • the lithium-doped silicon oxide composite material synthesized in step 2 is placed in an inert atmosphere furnace, an organic carbon source gas is introduced, and the carbon source undergoes a cracking reaction at a temperature of 400-1100 ° C.
  • a carbonaceous coating layer is formed on the surface of the doped silicon oxide composite material.
  • the step of achieving the coating of the carbonaceous material includes but is not limited to the above-mentioned cracking reaction of the gas organic carbon source, and may also be solid phase mixed carbon source coating, asphalt coating, hydrothermal reaction coating, oil bath coating, etc., It may also be resins, sugars, oils, fats, organic acids, organic acid esters, small-molecule alcohols, carbon nanotubes, graphene, etc., but the carbon source is in addition to the gaseous organic carbon source.
  • the thickness of the coating layer is 2 to 1000 nm.
  • Another method embodiment of the present invention provides a method for manufacturing the porous silicon-oxygen composite anode material in the second embodiment described above.
  • the production method mainly includes the following steps:
  • FIG. 7 it is a SEM image of the surface of the material.
  • the arrows in the figure indicate that the surface of the material has formed the porous channel structure on the particle surface through etching and dipping treatment in this embodiment.
  • Step 3 In-situ formation of non-lithium silicate to form a lithium-doped silicon oxide with a gradient structure, that is, to form a core 1 structure covering the intermediate layer 2:
  • step 2 Partially mix the lithium-doped silicon oxide and metal Mg powder of the porous structure prepared in step 2 at a high mass ratio of 100: 5 at a high speed, and roast for 1.5 hours at 850 ° C under an argon atmosphere. After cooling to room temperature, remove , A gradient structure of lithium-doped silicon oxide with non-lithium silicate as Mg2SiO4 formed in situ on the surface of the material is obtained.
  • step 3 Place the gradient-structured lithium-doped silicon oxide prepared in step 3 in an atmosphere furnace, pass the N2 to remove the remaining air in the furnace to ensure that the atmosphere in the furnace is an inert atmosphere, and then raise the temperature of the furnace to 850 ° C while passing Carbon source C2H2, after 1 hour of reaction, stop the flow of carbon source gas, and finally cool down to room temperature in an inert atmosphere, open the furnace, and take out the porous silicon-oxygen composite anode material.
  • step 5 may also be included, which is used to make the silicon-oxygen composite anode material into a secondary battery.
  • the prepared silicon-oxygen composite negative electrode material and commercial graphite G49 were mixed into 600mAh / g negative electrode material, and the conductive agent Super P, binder SBR, CMC were dispersed in deionized water according to a mass ratio of 95: 0.3: 3.2: 1.5.
  • the electrolyte is 1mol / L LiPF6 / EC + PC + DEC + EMC (Volume ratio 1: 0.3: 1: 1)
  • the separator is a PP / PE / PP three-layer separator with a thickness of 10um, which is made into a soft-pack battery of about 3.7Ah.
  • the soft pack battery can be used to test the full battery performance of the material.
  • a method for manufacturing the silicon-oxygen composite anode material in the above-mentioned third embodiment is provided.
  • the coating layer 3 of the silicon-oxygen composite anode material includes an organic polymer or a polymer dispersed coating to form a package. Cladding.
  • the manufacturing method of the polymer coating layer includes: dispersing 100 g of the product of step 2 in the first embodiment in 300 g of xylene solvent, adding 2 g of uncured epoxy resin particles, and stirring at 60 ° C. for 3 hours Then, ultrasonic dispersion was performed for 60 minutes, 0.5g of T31 curing agent was added, stirred for 2 hours, and spray-dried at 100 ° C to obtain the gradient-structured lithium-doped silicon oxide material coated with the polymer organic substance.
  • a method for manufacturing the silicon-oxygen composite anode material in the fourth embodiment described above is provided.
  • the polymer-coated layer 3 of the silicon-oxygen composite anode material not only covers the surface of the intermediate layer 2 but also It also penetrates and fills all the channels of the inner core 1 and the middle layer 2.
  • the manufacturing method of the polymer coating layer includes: dispersing 100 g of the product of step 3 in the second embodiment in 300 g of xylene solvent, adding 5 g of uncured epoxy resin particles, and stirring at 60 ° C. for 6 hours Then, after ultrasonic dispersion for 60 minutes, adding 2g of T31 curing agent, stirring for 2 hours, spray drying at 100 ° C, the gradient structure lithium-doped silicon oxide material coated with the polymer can be obtained.
  • a method for manufacturing the silicon-oxygen composite anode material in the above fifth embodiment is also provided.
  • the coating layer 3 of the silicon-oxygen composite anode material is directly coated on the surface of the inner core 1 and is completely Fill some or all of the holes of the inner core 1.
  • the manufacturing method of the polymer coating layer includes: dissolving cetyltrimethylammonium bromide (CTAB, (C16H33) N (CH3) 3Br, 7.3g) in HCl in an ice water bath (0-4 ° C) (500mL) solution, add 100g of the first embodiment of the product of step 1 lithium-doped silicon oxide, then add pyrrole monomer (Pyrrole, 8.3mL), first super-dispersed for 30 minutes, and then stirred for 2 hours, then Ammonium sulfate (APS, 13.7g, dissolved in 100ml of 1mol / L hydrochloric acid) solution was added dropwise, maintaining stirring, kept at 0-4 °C for 24h after filtration, the gray-green precipitate obtained with 1mol / L HCl solution was washed three times, and then washed with purified water until the solution was colorless and neutral, and then the precipitate was dried at 80 °C for 24h, you can get a polymer structure gradient
  • the physical and chemical parameters of the silicon-oxygen composite anode material (Poly Li doped SiO x ) with an organic coating layer and the partial lithium doped silicon oxide material (Li doped SiOx) with no pores and no gradient structure in the above fifth embodiment For example, the following table 1:
  • the silicon-oxygen composite anode material with a gradient structure in the first embodiment, the silicon-oxygen composite anode material with a porous structure in the second embodiment, and the silicon-oxygen composite anode material with an organic coating layer in the third embodiment are all Compared with the ordinary non-porous, non-gradient structure, the material performance of some lithium-doped silicon oxide materials has been significantly improved, especially in terms of processing performance, half-electrode sheet expansion rate and 500-cycle cycle retention rate, the specific analysis is as follows :
  • the gradient-structured lithium-doped silicon oxide of the silicon-oxygen composite negative electrode material in the first embodiment forms in-situ on the basis of the original lithium-doped silicon oxide material, insoluble or non-alkaline or weakly alkaline Of non-lithium silicate layer.
  • the non-lithium silicate layer itself is weakly alkaline, on the other hand, the composite layer can ease the dissolution of the water-soluble strong alkaline lithium silicate in the lithium-doped silicon oxide material in the water, playing a slow-release effect, effective
  • the pH value of the material is reduced, and the slurry processing performance of the negative electrode material is reflected.
  • the problems of gas production and easy coating drop of the traditional lithium-doped silicon oxide slurry are well solved.
  • the porous channels of the silicon-oxygen composite anode material and the gradient structure lithium-doped silicon oxide are used to etch and impregnate the lithium-doped silicon oxide before synthesis of the gradient structure material to manufacture a radial horn
  • the water-soluble lithium silicate at a certain depth on the surface of the silicon oxide can be removed, and on the basis of this, the in-situ construction of the non-lithium silicate gradient structure can be performed to achieve a better effect of lowering the pH value.
  • the multi-channel structure can effectively relieve the stress caused by the expansion of the silicon-based material of the outer layer of silicon oxide and ensure the integrity of the structure.
  • the expansion rate of the semi-electrode sheet of Porous Mg-Lidoped SiOx is 21%, which is significantly lower than that of Example 1 and Example 3.
  • the porous channel structure can enhance the retention of electrolyte in the material, provide a rich lithium ion diffusion channel, promote lithium ion transmission, and improve the rate performance of the battery cell.
  • the polymer coating layer formed on the surface of the silicon-oxygen composite anode material can prevent the strong alkaline lithium silicate and / or residual lithium in the core from dissolving in the water during the slurry preparation process. It plays the role of reducing the water-soluble pH value of the material and increasing the stability of the slurry, and the polymer coating layer is evenly coated on the surface of the material, which has a certain inhibitory effect on the volume expansion of the material during the charging and discharging process.
  • the polymer coating layer formed on the material surface and pores of the silicon-oxygen composite anode material in the fourth embodiment can prevent the strong alkaline lithium silicate and / or residual lithium in the inner core during the slurry preparation process. Dissolved in water, it plays the role of reducing the water-soluble pH value of the material and increasing the stability of the slurry, and the polymer also permeates and fills all the pores of the inner core 1 and the middle layer 2, which inhibits the volume expansion of the material during charging and discharging. effect.
  • the polymerization reaction of the silicon-oxygen composite anode material in the fifth embodiment occurs in a hydrochloric acid solution.
  • Hydrochloric acid can completely dissolve the alkaline water-soluble components in the lithium-doped silicon oxide, which not only effectively reduces the pH of the material
  • the mass ratio of the active material silicon grains is increased, and the formed pores will be automatically filled with organic small molecule reactants.
  • the resulting polymer will not only be evenly coated On the surface of the material, these holes will be filled, which can effectively buffer the volume change of the material during charging and discharging.
  • the polymer polypyrrole produced in this embodiment also has conductivity and lithium storage activities, and has a certain effect on improving the electrical performance of doped silicon oxide.
  • the battery cycle data corresponding to the test standard cell shows that the lithium ion battery prepared using the materials in Examples 1, 2, and 3 and the part of the non-porous, non-gradient structured partially lithium-doped silicon oxide material cycle for 500 weeks After that, the capacity retention ratios were 76%, 90%, 90%, and 66%, respectively.
  • the cell cycle performance of the gradient-structured lithium-doped silicon oxide material was significantly better than that in the sixth embodiment.
  • the treated lithium-doped silicon oxide battery, and the second and third embodiments respectively adopt the porous structure of the present invention and the polymer coating, the battery has the best cycle performance.
  • lithium-doped silicon oxide material has better processing performance, lower material expansion, stronger structural stability, and lower surface Side reactions, and less lithium ion consumption due to structural damage, ultimately bring a comprehensive improvement in cycle performance.
  • the polymer coating has a good slurry stabilizing effect, and effectively suppresses the expansion of the pole piece, which improves the cycle performance of the battery core.

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Abstract

一种硅氧复合负极材料，用于制作电动汽车、智能车或者终端的锂电池的负极，所述负极材料包括内核、包覆在所述内核外面的包覆层以及位于所述内核以及所述包覆层之间的中间层，其中所述中间层包括所述非锂硅酸盐，所述非锂硅酸盐是指非锂硅酸盐，所述非锂硅酸盐在所述中间层中的质量含量占分布由是由所述中间层向所述内核递减。所述递减包括由所述中间层向所述内核呈梯度减少，所述梯度减少是指距离所述内核中心距离相同的圆周上的质量占比相同，随着与所述内核中心的距离减小而所述质量占比逐级减少。所述非锂硅酸盐在内核的外层原位生成，具有非水溶性或非碱性或弱碱性的致密结构，能有效缓解内部水溶性硅酸锂的溶解，降低所述鬼眼复合负极材料的pH值。

Description

一种硅氧复合负极材料及其制作方法 技术领域
本发明涉及二次电池技术领域，特别是涉及一种硅氧复合负极材料及其制作方法。
背景技术
传统石墨负极材料在商业的锂离子电池中广泛使用，但因其理论克比容量较低，仅为372mAh/g的特点，限制了单纯石墨负极在高能量密度、长循环电池开发中的长足应用。因此人们把目光转向容量更高的硅基、锡基负极材料。在硅基材料中，氧化硅材料的首次嵌锂容量为2615mAh/g，虽然比单质硅的理论嵌锂容量4200mAh/g低很多，但仍远高于传统石墨负极，与单质硅300％的嵌锂/脱锂体积膨胀相比，氧化硅的膨胀只有160％。
此外，氧化硅在锂离子嵌入过程中会形成不可逆的氧化锂(Li 2O)和硅酸锂(Li xSi yO z)副产物，其可作为天然缓冲层缓解硅锂合金Li xSi在锂离子嵌入时的体积膨胀，避免硅材料膨胀过大引起的颗粒破碎、材料表面SEI膜不稳定、持续消耗电解液中活性Li离子以及最终的循环寿命衰减过快等问题，因此以氧化硅为负极的电池循环寿命和容量保持率往往比普通硅碳材料更高。
然而，氧化硅在电池首次充电嵌锂的过程中吸收锂离子会形成副产物氧化锂和硅酸锂，该副产物在放电过程中不能完全脱出其在充电过程吸收的锂离子。这种不可逆反应会造成电池中大量活性锂离子的损失，形成不可逆容量。因此，传统氧化硅负极的首效低于80％，正极材料的首效一般大于85％，但是正负极材料匹配时会造成正极材料中提供的锂离子在负极牺牲形成不可逆容量，导致正极克容量发挥不足，影响电池整体容量和能量密度。因此如何提高负极材料氧化硅的首效是当下迫切需要解决的问题。
发明内容
鉴于此，本发明实施例提供一种硅氧复合负极材料及其制作方法，能够有效解决现有硅氧复合负极材料首效低的问题。
本发明实施例提供一种硅氧复合负极材料，用于制作锂电池的负极，所述负极材料包括内核、包覆在所述内核外面的包覆层以及位于所述内核以及所述包覆层之间的中间层，其中所述中间层包括所述非锂硅酸盐，所述非锂硅酸盐在所述中间层中的质量含量占分布由是由所述中间层向所述内核递减。所述递减包括由所述中间层向所述内核呈梯度减少，所述梯度减少是指距离所述内核中心距离相同的圆周上的质量占比相同，随着与所述内核中心的距离减小而所述质量占比逐级减少。
所述非锂硅酸盐在内核的外层原位生成，具有非水溶性或非碱性或弱碱性的致密结构，能有效缓解内部水溶性硅酸锂的溶解，降低所述鬼眼复合负极材料的pH值。
通过对硅酸盐的梯度梯度结构设计，能降低复合负极材料的pH值，使其保持较好的加工性能，能同时兼顾材料的电化学性能和加工稳定性。
所述中间层还包含氧化硅，其化学式是SiO x，其中0.6≤x≤2，其中x为本化学式SiO x独立变量，所述氧化硅质量含量分布与所述非锂硅酸盐相反。
所述内核包括纳米硅、氧化硅和硅酸锂的混合物，所述氧化硅在整个内核中的质量含量 占比分布是由沿着所述包覆层向内核的径向方向上呈梯度增加，而所述硅酸锂在所述内核中的质量含量占分布由是所述包覆层向内核呈梯度减少。
所述部分锂掺杂的氧化硅结构，其中纳米硅、硅酸盐的含量为由外向内递减，氧化硅的含量为由外向内递增，这种梯度结构可以防止材料内核中因掺杂反应生成的纳米硅含量过多，能有效减少内核在充放电过程中内核承担的应力，避免长时间循环造成内核破碎。
所述内核以及中间层上开设多个孔道，所述孔道由中间层的表面由外向内延伸，而且所述孔道成锥形孔状，所述孔道的孔径由所述中间层的表面向所述内1中心逐渐缩小。
所述从材料的颗粒表面向内核方向延伸、非完全连通的“喇叭状”孔道结构，能有效缓解高首效氧化硅颗粒外层在充放电过程中的膨胀；而且所述孔道与孔道间未形成完全的联通结构，能防止孔道过深造成电解液与材料内部副反应过多引起的结构坍塌和性能衰减；另外，所述多孔结构提供的多锂离子扩散通道，能提升材料的快充能力。
所述中间层是在内核表面引入非锂金属盐发生反应生成的混合物层，所述非锂硅酸盐在所述内核材料的表面原位形成，能保证材料结构的稳定性，同时非水溶性/非碱性/弱碱性的致密结构能有效缓解内部水溶性硅酸锂的溶解，降低材料的pH值。
所述包覆层为碳质材料，所述碳质材料为单纯由无定型碳，或者所述碳质材料为所述无定型碳及镶嵌在所述无定型的碳纳米管或石墨烯组成的混合物。
所述包覆层包括还可以由有机物聚合或高分子分散包覆形成包覆层，所述包覆层厚度为2～200nm。
所述碳质包覆层或有机聚合物包覆层，能增加材料的电子电导，同时包覆层结构能防止电解液与活性材料直接接触产生过多表面副反应，减少不可逆容量和电池中锂离子的损耗，此外，包覆层能对材料在充放电过程中的膨胀收缩起到一定抑制作用，综合起到提升电池的循环性能的效果。
附图说明
图1为使用本发明实施例的硅氧复合负极材料的电池结构图。
图2为本发明第一实施例提供氧复合负极材料结构示意图。
图3为本发明第一实施例提供硅氧复合负极材料成分质量浓度分布图。
图4为本发明第一实施例提供的硅氧复合负极材料样品的切面电镜图。
图5为本发明第二实施例提供硅氧复合负极材料的多孔结构示意图。
图6是本发明一方法实施例提供的硅氧复合负极材料的制作流程图。
图7为本发明第二实施例提供硅氧复合负极材料的表面电镜图。
图8为测试各实施例的硅氧复合负极材料制作的电池的循环数据图表。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例进行说明。
本发明实施例主要涉及一种新的硅氧复合负极材料，所述材料用于制作锂电池的负极。所述锂电池的主要用于终端消费产品，如各种手机、平板电脑、笔记本电脑以及其它可穿戴或可移动的电子设备。
如图1所示，所述锂电池的核心部件包括正极材料101、负极材料102、电解液103、隔膜104以及相应的连通辅件和回路。所述正负极材料可以脱嵌锂离子实现能量的存储和释放， 所述电解液是锂离子在正负极之间传输的载体，所述隔膜可透过锂离子但不导电从而将正负极隔开防止短路。所述正复合负极材料通常对锂电池的储能功用大小、其电芯的能量密度、循环性能及安全性等关键性能因素起到决定性的作用。
本发明实施例的负极材料聚焦高克比容量(mAh/g)的氧化硅复合负极材料。在通过锂掺杂形成的硅酸锂盐来改变材料的晶体结构，减少不可逆反应，从而在保持氧化硅材料较高克比容量的基础上提升其首效，达到提升电芯能量密度的目标。
同时，通过对内核以及硅酸盐的梯度梯度结构设计，能降低复合负极材料的pH值，使其保持较好的加工性能，能同时兼顾材料的电化学性能和加工稳定性。此外，本发明实施例的复合负极材料表面具有径向锥孔结构，可以缓解材料在充放电过程中的体积膨胀以及提供更丰富的锂离子传输通道，有利于电池长循环寿命的提升，而提高产品的整体竞争力。
一、材料实施例
如图2所示，本发明第一实施例的硅氧复合负极材料包括内核1、包覆在所述内核1外面的包覆层3以及位于内核1以及包覆层3之间的中间层2。
所述内核1为锂掺杂氧化硅内核，其中所述锂掺杂的氧化硅内核为多种材料形成的混合物。所述内核1包括纳米硅(nano Si)、氧化硅和硅酸锂的混合物，其中所述混合物的颗粒半径r大小为50nm～20um。
所述氧化硅的化学式是SiO x，其中0.6≤x≤2，其中x为本化学式SiO x独立变量，与其它化学式的x不存在关联关系。后面化学式中使用到的，用于表示分子数比的下标变量也与x的原则相同，在不同化学式中的相同字母如x、y等不具有关联关系，只是为了方便表述而不予区分而已。如图3所示，所述氧化硅在整个内核中的质量含量占比分布是由沿着所述包覆层3向内核2的径向方向上递增，其中所述图3中的外壳是指所述包覆层3。所述递增可以是梯度增加，比如，可以指距离所述氧化硅负极材料的中心距离相同的圆周上的质量占比相同，随着与所述负极材料中心的距离变化而逐渐或逐级变化。
所述硅酸锂的化学式为Li 2xSi yO (x+2y)，是锂掺杂氧化硅反应后形成的产物，是多种硅酸盐的混合物，其组成包括但不限于Li 4SiO 4、Li 2SiO 3以及Li 2Si 2O 5等。所述硅酸锂在所述内核1中的质量含量占分布由是所述包覆层3向内核1呈梯度减少，也就是所述内核1最外层的硅酸锂质量占比最高，然后向所述内核1中心逐层降低。
此外，所述内核1以及所述中间层2还包括C、H、N、B、P、S、Cl以及F等非金属掺杂元素，并且所述非金属掺杂元素在内核1中呈梯度分布，所述梯度分布为从中间层2外向内核1中心递减。
所述C、H、N、B、P、S、Cl以及F等非金属元素，以掺杂形态存在于内核1以及所述中间层2混合物的任何一种或多种化合物中，所述掺杂元素相对于被掺杂物质的摩尔占比小于5％。
所述梯度分布是根据扩散原则，在制作所述内核1时控制锂源的添加量和合成温度，锂源在材料中由外向内的浓度为梯度递减，因此所述内核1中纳米硅、硅酸盐的含量为由外向内递减，氧化硅的含量为由外向内递增。所述梯度分布形成的内核结构可以防止材料内核中因掺杂反应生成的纳米硅含量过多，能有效减少内核在充放电过程中内核承担的应力，避免长时间循环造成内核破碎。此外，所述硅氧复合负极材料的锂掺杂成分主要包含在硅酸锂以及纳米锂中，在所述内核1中的质量含量占分布由是所述包覆层3向内核1呈梯度减少，也 就是所述内壳1最外层的掺杂锂元素成分质量占比最高，然后向所述内核1中心逐层降低。
所述中间层2在内核1表面原位生成非锂硅酸盐，也就是所述中间层2是在内核1表面引入非锂金属盐发生反应生成的混合物层。所述中间层2包括非锂硅酸盐、纳米硅、氧化硅和硅酸锂，所述非锂硅酸盐是指除了硅酸锂之外的掺杂金属硅酸盐。所述非锂硅酸盐的化学式为M xSi yO z，其中所述M包括Al、Ca、Mg、Be、Sr、Ba、Ti等金属元素中的一种或多种的组合。如图3所示，所述非锂硅酸盐在所述中间层2中的质量含量占分布由是所述包覆层3向内核1呈梯度减少，也就是所述中间层2最外层的非锂硅酸盐的质量占比最高，然后越靠近所述内核1中心位置的非锂硅酸盐在整个所述中间层2中的质量占比就越低，其中图中所示的外壳是指所述包覆层3。M元素和所述非锂硅酸盐的浓度分布是一致的。所述非锂硅酸盐在内核1的外层原位生成，具有非水溶性或非碱性或弱碱性的致密结构，能有效缓解内部水溶性硅酸锂的溶解，降低所述鬼眼复合负极材料的pH值。所述中间层2还包含氧化硅，其化学式是SiO x，其中0.6≤x≤2，其中x为本化学式SiO x独立变量，所述氧化硅质量含量分布与所述非锂硅酸盐相反。所述氧化硅在所述中间层2中的质量含量占分布由是所述包覆层3向内核1呈梯度增加，也就是所述中间层2最外层的非锂硅酸盐的质量占比最少，然后越靠近所述内核1中心位置的非锂硅酸盐在整个所述中间层2中的质量占比就越高。所述中间层也包括纳米硅、氧化硅和硅酸锂的混合物。
如图4所示为所述硅氧复合负极材料样品的切面二次电子像图和元素Mg(M xSi yO z中的M为Mg时)的分布图，切面图可以观察到样品内部的结构分布，其中图4为电镜图利用二次电子成像和倍散电子成像，主要用于表面微观形貌观察或者表面元素分布观察。所述样品切面图中有明显的深浅灰色区分，浅灰色部分为部分锂掺杂氧化硅表面原位形成的非锂硅酸盐Mg2SiO4，图4的右边部分中对应可见Mg元素的分布和左边部分的轮廓一致，且从右边部分中可以看出，Mg的浓度是从外层向内核区域递减的梯度分布。
所述包覆层3并非本发明实施例中硅氧复合负极材料的必须组成，在一些实施例中可以没有所述包覆层3。在一些实施例中，所述包覆层3为碳质材料，在所述硅氧复合负极材料的最外层形成包覆层结构，所述包覆层厚度可以为2～1000nm。所述碳质材料为碳源裂解形成的无定型碳，或者是无定型碳及镶嵌在其中的碳纳米管或/和石墨烯组成的混合物。所述包覆层3可以是碳质材料和/或有机聚合物包覆层，所述碳质材料包覆层能增加材料的电子电导，同时包覆层结构能防止电解液与活性材料直接接触产生过多表面副反应，减少不可逆容量和电池中锂离子的损耗。
如图5所示，本发明的第二实施例中的硅氧复合负极材料硅氧复合负极材料，其内核1以及中间层2上还设置有多孔结构。所述硅氧复合负极材料上开设多个孔道12，所述孔道12由中间层2的表面由外向内延伸，而且所述孔道12成锥形孔状，所述孔道12的孔径由所述中间层2的表面向所述内核1中心逐渐缩小，也就是所述孔径沿着由所述中间层2的表面向所述内核1内的方向呈梯度缩小趋势。例如，所述孔道12在中间层2表面的开口孔径大于位于所述内核1部分的孔径，也就是D out>D in，而且所述孔道12的深度小于所述内核1混合物的颗粒半径r，也就是D depth<r，而且10nm<D depth<500nm。
在一些实施例中，所述孔道12的开口均匀分布于所述中间层2的表面，每一孔道12沿着所述中间层2的表面向所述内核1中心的径向延伸。
因为所述内核1的梯度锂掺杂氧化硅的结构特点为从表面向颗粒轴心方向掺杂浓度递减，在内核1表面的纳米Si颗粒分布最多，由中间层2以及内核1表面向轴心方向衍生的多孔道 结构设计，能缓解高首效氧化硅颗粒外层在充放电过程中的膨胀，且所述孔道12与孔道12间未形成完全的联通结构，能防止孔道12过深造成电解液与材料内部副反应过多引起的结构坍塌和性能衰减。另外，所述多孔道结构提供更多锂离子扩散通道，能提升材料的快充能力。
在本发明的第三实施例中所述包覆层3包括由有机物聚合或高分子分散包覆形成的聚合物包覆层。
在本发明的第四实施例中所述聚合物包覆层3不仅包覆在中间层2表面，而且还完全填充所述内核1和中间层2的所有孔道12。在一些实施例中，所述包覆层3仅填充部分所述孔道12。
在本发明的第五实施例中所述聚合物包覆层3直接包覆在内核1表面，而且还完全填充所述内核1的所有孔道12。在一些实施例中，所述包覆层3仅填充部分孔道12。
二、方法实施例
如图6所示，本发明一方法实施例提供第一实施例中硅氧复合负极材料的制作方法。所述制作方法主要包括以下步骤：
步骤1、部分锂掺杂氧化硅制备：将氧化硅与锂源按照一定配比混合均匀后转移到匣钵中，在惰性气氛或还原气氛环境下焙烧。
具体为将氧化硅与锂源按照一定配比混合均匀后转移到匣钵中(0.1≤n Li/n Si≤1.0，所述n Li/n Si为锂离子与氧化硅之间的摩尔数比)，然后将所述匣钵转移到惰性气氛或还原气氛的高温炉中，进行焙烧反应，焙烧温度在300～900℃温度区间内，可得到部分锂掺杂的氧化硅，也就是硅酸锂与氧化硅的混合体。所述锂化掺杂使用的锂源为锂盐，所述锂盐主要包括LiH、LiAlH 4、Li 2CO 3、LiNO 3、LiAc以及LiOH中的一种或多种。
步骤2、原位合成非锂硅酸盐：将已经部分锂化掺杂的氧化硅和非锂金属或金属盐按一定比例均匀混合后进行焙烧。
具体为将已经部分锂化掺杂的氧化硅和非锂金属或金属盐按一定比例混合均匀获得混合物，所述混合物转移到匣钵中进入惰性气氛或还原气氛的高温炉中，进行400～1000℃温度区间内的焙烧，在部分锂掺杂氧化硅或多孔的部分锂掺杂氧化硅表面原位生成非锂硅酸盐，得到分层结构且梯度分布的锂掺杂氧化硅复合材料，所述分层结构是指所述锂掺杂氧化硅复合材料包括上述一实施例中的内核1和中间层2的结构。
所述非锂硅酸盐结构式为M xSi yO z，M包括但不限于Al、Ca、Mg、Be、Sr、Ba、Ti、Zr等金属元素的一种或多种，M还包括但不限于所述金属元素的单质金属或金属盐，其中金属元素M与Si的摩尔比满足0.01≤n M/n Si≤0.3。
步骤3、碳质材料二次包覆：将步骤2合成的所述锂掺杂氧化硅复合材料放入惰性气氛炉中，通入有机碳源气体，在高温度下发生裂解反应，从而在所述锂掺杂氧化硅复合材料表面形成碳质包覆层。
具体为将步骤2合成的所述锂掺杂氧化硅复合材料放入惰性气氛炉中，通入有机碳源气体，在400～1100℃的温度下使碳源发生裂解反应，从而在所述锂掺杂氧化硅复合材料表面形成碳质包覆层。
实现所述碳质材料包覆的步骤包括但不限于上述气体有机碳源裂解反应，也可以是固相混合碳源包覆、沥青包覆、水热反应包覆、油浴法包覆等，也可以是树脂、糖类、油脂、有机酸、有机酸酯、小分子醇以及碳纳米管、石墨烯等，但是碳源除气体有机碳源外。所述包 覆层厚度为2～1000nm。
本发明另一方法实施例提供上述第二实施例中多孔硅氧复合负极材料的制作方法。所述制作方法主要包括以下步骤：
步骤1、部分锂掺杂氧化硅制备：
将表面碳包覆量为4.3％且平均粒径为5μm的氧化硅SiOx(x＝1)及作为锂源的氢化锂LiH按照质量比100:(8～10)的比例混合后获得混合物，其中所述混合物需在氩气氛围中用混合机混合至少20min保证样品均匀；
将所述混合物转移到匣钵中，并将所述匣钵转移进入气氛炉内，通入氩气，于700～800℃的温度中反应2小时，冷却至室温后，将所述匣钵取出得到部分锂掺杂的氧化硅材料。
步骤2、多孔道结构制备：
取500g步骤1中制备的所述部分锂掺杂氧化硅材料，加入1L 0.2M NaOH水溶液，以转速500r/min搅拌分散1h获得混合材料，对所述混合材料进行造孔刻蚀；处理完毕后对所述混合材料进行抽滤，抽滤完毕后取下滤饼，并向其中加入1L水，以转速500r/min搅拌分散1h，然后抽滤；通过水洗洗去未反应的NaOH以及反应副产物，并对剩下的部分锂掺杂氧化硅中的硅酸锂盐进行部分溶解，也形成孔道结构。
如此重复进行3次对所述混合材料进行抽滤、后加入水和抽滤的操作后将滤饼取出放入温箱中100℃烘烤至干燥，得到多孔道结构的部分锂掺杂氧化硅。
如图7所示，为材料的表面电镜图，图中箭头所指为材料表面通过本实施例中刻蚀和浸渍处理，在颗粒表面形成了形成的多孔道结构。
步骤3、原位形成非锂硅酸盐形成梯度结构的锂掺杂氧化硅，也就是形成包覆所述中间层2的内核1结构：
将步骤2制备得到的所述多孔道结构的部分锂掺杂氧化硅与金属Mg粉按质量比100:5的比例高速混合均匀，在氩气气氛下850℃焙烧1.5h，冷却至室温后取出，得到在材料表面原位形成非锂硅酸盐为Mg2SiO4的梯度结构锂掺杂氧化硅。
步骤4、碳材料包覆层制作：
将步骤3制备得到的所述梯度结构锂掺杂氧化硅置于气氛炉中，通入N2排除炉中残留的空气保证炉内气氛为惰性气氛，再将炉温升至850℃，同时通入碳源C2H2，反应1h后停止碳源气体的通入，最后在惰性气氛中冷却至室温后打开炉膛，取出所述多孔硅氧复合负极材料。
在本申请的一些实施例中还可以包括步骤5，用于将所述硅氧复合负极材料制作成二次电池。
步骤5、二次电池的制备：
制备得到所述硅氧复合负极材料与商业石墨G49混成600mAh/g的负极材料，与导电剂Super P、粘结剂SBR、CMC，按照质量比95:0.3:3.2:1.5分散于去离子水中，搅拌均匀，得到电极浆料；再在铜箔表面涂布，85℃烘干，得到负极电极片；再配合商用钴酸锂正极材料，电解液为1mol/L LiPF6/EC+PC+DEC+EMC(体积比1:0.3:1:1)，隔膜为PP/PE/PP三层隔膜，厚度为10um，制作成3.7Ah左右的软包电池。所述软包电池可用于测试材料的全电池性能。
在本发明一些方法实施例中提供了上述第三实施例中的硅氧复合负极材料的制作方法，所述硅氧复合负极材料的包覆层3包括由有机物聚合或高分子分散包覆形成包覆层。
所述高分子聚合物包覆层的制作方法包括：将第一实施例中步骤2的产物100g分散在 300g二甲苯溶剂中，加入2g未固化处理的环氧树脂颗粒，60℃下搅拌3小时，再超声分散60分钟，加入T31固化剂0.5g，搅拌2小时，100℃下喷雾干燥，即可得到所述高分子有机物包覆的梯度结构锂掺杂氧化硅材料。
在本发明一些方法实施例中提供了上述第四实施例中的硅氧复合负极材料的制作方法，所述硅氧复合负极材料的聚合物包覆层3不仅包覆在中间层2表面，而且还渗透填充了内核1和中间层2的所有孔道。
所述高分子聚合物包覆层的制作方法包括：将第二实施例中步骤3的产物100g分散在300g二甲苯溶剂中，加入5g未固化处理的环氧树脂颗粒，60℃下搅拌6小时，再超声分散60分钟，加入T31固化剂2g，搅拌2小时，100℃下喷雾干燥，即可得到所述高分子聚合物包覆的梯度结构锂掺杂氧化硅材料。
在本发明一些方法实施例中还提供了上述第五实施例中的硅氧复合负极材料的制作方法，所述硅氧复合负极材料的包覆层3直接包覆在内核1表面，而且还完全填充所述内核1的部分或所有孔道。
所述聚合物包覆层的制作方法包括：将十六烷基三甲基溴化铵(CTAB，(C16H33)N(CH3)3Br，7.3g)溶解在冰水浴(0-4℃)的HCl(500mL)溶液中，加入100g第一实施例中步骤1的产物锂掺杂氧化硅，然后加入吡咯单体(Pyrrole，8.3mL)，先超生分散30分钟，再搅拌2小时后，再将过硫酸铵(APS，13.7g，溶解在100ml 1mol/L的盐酸中)溶液逐滴加入其中，保持搅拌状态，在0-4℃下保温反应24h后过滤，将得到的灰绿色色沉淀物用1mol/L的HCl溶液洗涤三次，再用纯净水洗涤至溶液呈无色中性，接着把沉淀物在80℃下干燥24h，即可得到高分子聚合物包覆的梯度结构锂掺杂氧化硅材料。
上述第一实施例中具有梯度结构的硅氧复合负极材料(Mg-Li doped SiOx)、上述第二实施例中具有多孔结构的硅氧复合负极材料(Porous Mg-Li doped SiOx)、上述第三实施例中具有有机物包覆层的硅氧复合负极材料(Poly Mg-Li doped SiOx)、上述第四实施例中具有有机物包覆层的硅氧复合负极材料(Poly2 Mg-Li doped SiO x)、上述第五实施例中具有有机物包覆层的硅氧复合负极材料(Poly Li doped SiO x)以及对比普通无孔道、无梯度结构的部分锂掺杂氧化硅材料(Li doped SiOx)的物理化学参数对比如下表1：
Figure PCTCN2019120043-appb-000001
表1所有实施例基本特性对比
可见，上述第一实施例中具有梯度结构的硅氧复合负极材料、第二实施例中具有多孔结构的硅氧复合负极材料以及第三实施例中具有有机物包覆层的硅氧复合负极材料均比普通无孔道、无梯度结构的部分锂掺杂氧化硅材料的材料性能有显著的提升，特别是在加工性能、半电极片膨胀率以及500周循环保持率上面有显著的优势，具体分析如下：
1、所述第一实施例中硅氧复合负极材料的梯度结构的锂掺杂氧化硅，在原始锂掺杂氧化硅材料的基础上原位形成了非水溶性或无碱性或弱碱性的非锂硅酸盐层。一方面，非锂硅酸盐层本身为弱碱性，另一方面该复合层能缓解锂掺杂氧化硅材料中的水溶强碱性硅酸锂在水中的溶解，起到了缓释作用，有效降低了材料的pH值，而体现到负极材料的浆料加工性能方面，传统锂掺杂氧化硅制浆浆料的产气、涂布易掉料等问题得到了很好的解决。
2、所述第二实施例中硅氧复合负极材料的多孔道以及梯度结构锂掺杂氧化硅，在进行梯度结构材料合成前对锂掺杂的氧化硅进行刻蚀和浸渍处理制造径向喇叭孔，造孔过程中能将氧化硅表面一定深度的水溶性硅酸锂除去，在此基础上再进行非锂硅酸盐梯度结构的原位构建，能起到更好降pH值的效果。同时，多孔道结构能有效缓氧化硅外层硅基材料膨胀产生的应力并保证结构的完整性。从表1的实验数据可看到，Porous Mg-Li doped SiOx(实施例二)的半电极片膨胀率为21％，相比实施例一和实施例三有明显下降。除以上有益效果外，多孔道结构能提升电解液在材料中的保有量，提供丰富的锂离子扩散通道，促进锂离子传输，提高电芯的倍率性能。
3、所述第三实施例中硅氧复合负极材料的材料表面形成的聚合物包覆层能防止内核中的强碱性硅酸锂和/或残锂在浆料制备过程中在水中溶解，起到了降低材料水溶性pH值、增加浆料稳定性的作用，且聚合物包覆层在材料表面均匀包覆，对材料在充放电过程中的体积膨胀有一定抑制作用。
4、所述第四实施例中硅氧复合负极材料的材料表面和孔道中形成的聚合物包覆层能防止内核中的强碱性硅酸锂和/或残锂在浆料制备过程中在水中溶解，起到了降低材料水溶性pH值、增加浆料稳定性的作用，而且聚合物还渗透填充了内核1和中间层2的所有孔道，对材料在充放电过程中的体积膨胀有一定抑制作用。
5、所述第五实施例中硅氧复合负极材料的聚合反应发生在盐酸溶液中，盐酸能够较为彻底的溶解锂掺杂氧化硅里面的碱性水溶性成分，不仅有效地降低了材料的pH值，而且碱性成分被溶解后，活性物质硅晶粒的质量占比提升，形成的孔道会被有机小分子反应物自动填充，加入聚合反应引发剂后，生成的高分子不仅会均匀包覆在材料表面，而且会填充这些孔道，可有效效缓冲材料在充放电过程中的体积变化。本实施例中生成的高分子聚吡咯还具有导电和储锂活性，对提升掺杂氧化硅的电性能有一定作用。
如图8测试标准电芯对应的电池循环数据表明，采用实施例一、二、三以及所述普通无孔道、无梯度结构的部分锂掺杂氧化硅材料中材料制备的锂离子电池循环500周之后的容量保持率分别为76％、90％、90％、66％，实施例一、二、三采用梯度结构锂掺杂氧化硅材料所制作的电芯循环性能明显优于实施例六中未做处理的锂掺杂氧化硅的电芯，而且实施例二、和实施例三分别采用本发明的多孔道结构和聚合物包覆后，电芯循环性能表现最优异。原理上可以表明在经过非锂硅酸盐原位形成梯度结构和多孔道结构设计之后，锂掺杂氧化硅材料具有更好的加工性能、更低材料膨胀、更强结构稳定性、更低表面副反应，以及更少因结构破坏造成的锂离子消耗，最终带来了循环性能的综合提升效果。另外，聚合物包覆起到了很好的浆料稳定效果，并有效抑制了极片膨胀，提升了电芯的循环表现。
所属领域的技术人员可以清楚地了解到，为描述的方便和简洁，上述描述的系统、装置和单元的具体工作过程，可以参考前述方法实施例中的对应过程，在此不再赘述。
以上所述，仅为本发明的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本发明的保护范围之内。因此，本发明的保护范围应所述以权利要求的保护范围为准。

Claims (17)

  1. 一种硅氧复合负极材料，其特征在于，包括内核、包覆层以及位于所述内核以及所述包覆层之间的中间层；
    所述中间层包括非锂硅酸盐非锂硅酸盐非锂硅酸盐，所述非锂硅酸盐在所述中间层中的质量含量占分布是由所述中间层向所述内核递减。
  2. 如权利要求1所述的硅氧复合负极材料，其特征在于，所述非锂硅酸盐在所述中间层中的质量含量占分布由所述中间层向所述内核递减包括由所述中间层向所述内核呈梯度减少，所述梯度减少是指距离所述内核中心距离相同的圆周上的质量占比相同，随着与所述内核中心的距离减小而所述质量占比逐级减少。
  3. 如权利要求2所述的硅氧复合负极材料，其特征在于，所述非锂硅酸盐结构式为M xSi yO z，其中所述M包括Al、Ca、Mg、Be、Sr、Ba、Ti、Zr中的一种或多种的组合。
  4. 如权利要求3所述的硅氧复合负极材料，其特征在于，所述中间层在内核表面原位生成非锂硅酸盐，所述中间层是在内核表面引入第二相金属盐发生反应生成的混合物层。
  5. 如权利要求4所述的硅氧复合负极材料，其特征在于，所述中间层还包含氧化硅SiO x，其中0.6≤x≤2，其中x为所述SiO x独立变量，所述氧化硅在所述中间层中的质量含量占分布由是所述包覆层向内核呈递增。
  6. 如权利要求1至4任一项所述的硅氧复合负极材料，其特征在于，所述内核以及中间层上开设多个孔道，所述孔道由中间层的表面由向所述内核延伸，而且所述孔道成锥形孔状，所述孔道的孔径由所述中间层的表面向所述内1中心逐渐缩小。
  7. 如权利要求6所述的硅氧复合负极材料，其特征在于，所述内核以及所述中间层均包括纳米硅、氧化硅和硅酸锂的混合物，其中所述混合物的颗粒半径r，所述孔道的深度D depth小于所述内核混合物的颗粒半径r，而且10nm<D depth<500nm。
  8. 如权利要求7所述的硅氧复合负极材料，其特征在于，所述包覆层包覆在所述中间层表面且完全填充所有所述孔道。
  9. 如权利要求1至8任一项所述的硅氧复合负极材料，其特征在于，所述内核包括纳米硅、氧化硅和硅酸锂的混合物，所述氧化硅在整个内核中的质量含量占比分布是由沿着所述包覆层向内核的径向方向上呈梯度增加，而所述硅酸锂在所述内核中的质量含量占分布由是所述包覆层向内核呈梯度减少。
  10. 如权利要求9所述的硅氧复合负极材料，其特征在于，所述内核还包括C、H、N、B、P、S、Cl以及F中的一种或多种非金属掺杂元素，所述非金属掺杂元素在内核中呈梯度分布，所述梯度分布为从中间层外向内核中心递减。
  11. 如权利要求1至10任一项所述的硅氧复合负极材料，其特征在于，所述包覆层为碳质材料，所述碳质材料为单纯由无定型碳，或者所述碳质材料为所述无定型碳及镶嵌在所述无定型的碳纳米管或石墨烯组成的混合物。
  12. 如权利要求1至8任一项所述的硅氧复合负极材料，其特征在于，所述包覆层包括由有机物聚合或高分子分散包覆形成包覆层，所述包覆层厚度为2～200nm。
  13. 一种锂电池，其特征在于，包括正极材料、电解液、隔膜以及如权利要求1至12任一项所述的硅氧复合负极材料。
  14. 一种终端设备，充放电电路以及用电元件，其特征在于，还包括如权利要求13所述 的锂电池，所述锂电池与充放电电路连接，通过所述充放电电路进行充电或给所述用电元件供电。
  15. 一种硅氧复合负极材料的制作方法，所述方法包括：
    步骤一、将氧化硅与锂源按照混合均匀后转移到匣钵中，在惰性气氛或还原气氛环境下焙烧获得部分锂化掺杂的氧化硅；
    步骤二、将所述部分锂化掺杂的氧化硅和非锂金属，或将所述部分锂化掺杂的氧化硅和非锂金属盐均匀混合后进行焙烧，在所述部分锂化掺杂的氧化硅表面原位生成非锂硅酸盐，得到梯度分布的锂掺杂氧化硅复合材料；
    步骤三、将所述锂掺杂氧化硅复合材料放入惰性气氛炉中，通入有机碳源气体，在所述锂掺杂氧化硅复合材料表面形成碳质包覆层。
  16. 如权利要求11所述的硅氧复合负极材料，其特征在于，所述锂源为单质或锂盐，所述锂盐包括LiH、LiAlH 4、Li 2CO 3、LiNO 3、LiAc以及LiOH中的一种或多种。
  17. 如权利要求11或12所述的硅氧复合负极材料，其特征在于，所述非锂硅酸盐结构式为M xSi yO z，M包括但不限于Al、Ca、Mg、Be、Sr、Ba、Ti中的一种或多种元素，其中元素M与Si的摩尔比满足0.01≤n M/n Si≤0.3。
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