CN115064671A - Silica composite negative electrode material and preparation method thereof - Google Patents
Silica composite negative electrode material and preparation method thereof Download PDFInfo
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- CN115064671A CN115064671A CN202210702528.8A CN202210702528A CN115064671A CN 115064671 A CN115064671 A CN 115064671A CN 202210702528 A CN202210702528 A CN 202210702528A CN 115064671 A CN115064671 A CN 115064671A
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- 239000002131 composite material Substances 0.000 title claims abstract description 88
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 118
- 239000000377 silicon dioxide Substances 0.000 title description 12
- 238000002360 preparation method Methods 0.000 title description 4
- 239000010410 layer Substances 0.000 claims abstract description 97
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052912 lithium silicate Inorganic materials 0.000 claims abstract description 69
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- 239000011247 coating layer Substances 0.000 claims abstract description 52
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 46
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 41
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Images
Classifications
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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
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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
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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
- H01M4/48—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 silicon-oxygen composite negative electrode material is used for manufacturing a negative electrode of a lithium battery of an electric automobile, an intelligent automobile or a terminal, and comprises an inner core, a coating layer coated outside the inner core and an intermediate layer positioned between the inner core and the coating layer, wherein the intermediate layer comprises non-lithium silicate, the non-lithium silicate refers to non-lithium silicate, and the mass content of the non-lithium silicate in the intermediate layer is gradually decreased from the intermediate layer to the inner core. The descending includes gradient decrease from the middle layer to the kernel, the gradient decrease refers to the same mass ratio on the circumference with the same distance from the center of the kernel, and the mass ratio decreases gradually with the decrease of the distance from the center of the kernel. The non-lithium silicate is generated in situ on the outer layer of the inner core, has a compact structure which is not water-soluble or non-alkaline or alkalescent, can effectively relieve the dissolution of the internal water-soluble lithium silicate, and reduces the pH value of the silicon-oxygen composite negative electrode material.
Description
The present application is a divisional application, the original application having application number 201811481527.5, the original application date being 2018, 12 and 5, the entire content of the original application being incorporated by reference in the present application.
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a silicon-oxygen composite negative electrode material and a manufacturing method thereof.
Background
The traditional graphite cathode material is widely used in commercial lithium ion batteries, but due to the characteristic that the theoretical gram specific capacity is lower and is only 372mAh/g, the long-term application of a pure graphite cathode in the development of high-energy-density long-cycle batteries is limited. Therefore, people look to silicon-based and tin-based cathode materials with higher capacity. In the silicon-based material, the initial lithium intercalation capacity of the silicon oxide material is 2615mAh/g, although the initial lithium intercalation capacity is much lower than the theoretical lithium intercalation capacity of 4200mAh/g of the simple substance silicon, the initial lithium intercalation capacity is still far higher than that of the traditional graphite negative electrode, and compared with the lithium intercalation/lithium deintercalation volume expansion of 300% of the simple substance silicon, the expansion of the silicon oxide is only 160%.
In addition, silicon oxide forms irreversible lithium oxide (Li) during lithium ion intercalation 2 O) and lithium silicate (Li) x Si y O z ) By-products that can act as natural buffer layers to relieve silicon lithium alloy Li x The volume expansion of Si during lithium ion intercalation avoids the problems of particle breakage, unstable SEI film on the surface of the material, continuous consumption of active Li ions in electrolyte, too fast attenuation of the final cycle life and the like caused by over-expansion of silicon materials, so that the cycle life and the capacity retention rate of the battery taking silicon oxide as the negative electrode are often higher than those of common silicon-carbon materials.
However, the absorption of lithium ions by silicon oxide during the first charging of the battery results in the formation of lithium oxide and lithium silicate as by-products which do not completely remove the lithium ions absorbed during charging during discharge. This irreversible reaction can result in the loss of a significant amount of active lithium ions in the cell, resulting in irreversible capacity. Therefore, the first efficiency of the traditional silicon oxide negative electrode is lower than 80%, the first efficiency of the positive electrode material is generally larger than 85%, but when the positive electrode material and the negative electrode material are matched, lithium ions provided in the positive electrode material are sacrificed to form irreversible capacity at the negative electrode, so that the gram capacity of the positive electrode is not fully exerted, and the overall capacity and energy density of the battery are influenced. Therefore, how to improve the first effect of the negative electrode material silicon oxide is a problem which needs to be solved urgently.
Disclosure of Invention
In view of this, the embodiment of the invention provides a silicon-oxygen composite anode material and a manufacturing method thereof, which can effectively solve the problem that the existing silicon-oxygen composite anode material is low in first efficiency.
The embodiment of the invention provides a silicon-oxygen composite negative electrode material which is used for manufacturing a negative electrode of a lithium battery, and the negative electrode material comprises an inner core, a coating layer coated outside the inner core and an intermediate layer positioned between the inner core and the coating layer, wherein the intermediate layer comprises non-lithium silicate, and the mass content of the non-lithium silicate in the intermediate layer is gradually decreased from the intermediate layer to the inner core. The descending includes gradient decrease from the middle layer to the kernel, the gradient decrease refers to the same mass ratio on the circumference with the same distance from the center of the kernel, and the mass ratio decreases step by step with the decrease of the distance from the center of the kernel.
The non-lithium silicate is generated in situ on the outer layer of the inner core, has a compact structure which is not water-soluble or non-alkaline or alkalescent, can effectively relieve the dissolution of the internal water-soluble lithium silicate, and reduces the pH value of the silicon-oxygen composite negative electrode material.
Through the gradient structure design of the silicate, the pH value of the composite negative electrode material can be reduced, the composite negative electrode material can keep better processing performance, and the electrochemical performance and the processing stability of the material can be considered at the same time.
The intermediate layer further comprises silicon oxide of the formula SiO x Wherein x is more than or equal to 0.6 and less than or equal to 2, wherein x is the chemical formula SiO x Independent variables, the silica mass content distribution is the opposite of the non-lithium silicate.
The inner core comprises a mixture of nano silicon, silicon oxide and lithium silicate, the mass content proportion distribution of the silicon oxide in the whole inner core is increased in a gradient manner along the cladding layer to the radial direction of the inner core, and the mass content proportion distribution of the lithium silicate in the inner core is decreased in a gradient manner from the cladding layer to the inner core.
According to the partial lithium-doped silicon oxide structure, the content of nano silicon and silicate is decreased from outside to inside, and the content of silicon oxide is increased from outside to inside, so that the gradient structure can prevent the content of nano silicon generated in the material core due to doping reaction from being too high, the stress born by the core in the charging and discharging process can be effectively reduced, and the core is prevented from being broken due to long-time circulation.
The inner core and the middle layer are provided with a plurality of pore channels, the pore channels extend from the surface of the middle layer to the inside, the pore channels are in a conical hole shape, and the pore diameter of the pore channels is gradually reduced from the surface of the middle layer to the center of the inner core.
The horn-shaped pore channel structure which extends from the particle surface of the material to the core direction and is not completely communicated can effectively relieve the expansion of the outer layer of the high-first-efficiency silicon oxide particles in the charging and discharging process; and a complete communication structure is not formed between the pore canal and the pore canal, so that structural collapse and performance attenuation caused by excessive side reactions in the electrolyte and the material due to the deep pore canal can be prevented; in addition, the multi-lithium ion diffusion channel provided by the porous structure can improve the quick charge capacity of the material.
The intermediate layer is a mixture layer generated by introducing non-lithium metal salt to the surface of the inner core for reaction, the non-lithium silicate is formed in situ on the surface of the inner core material, the stability of the material structure can be ensured, and meanwhile, the dissolution of the internal water-soluble lithium silicate can be effectively relieved by the compact structure of water insolubility, non-alkalinity and alkalescence, and the pH value of the material is reduced.
The coating layer is made of a carbonaceous material, the carbonaceous material is made of amorphous carbon only, or the carbonaceous material is a mixture of the amorphous carbon and carbon nano tubes embedded in the amorphous carbon or graphene.
The coating layer can be formed by organic matter polymerization or macromolecule dispersion coating, and the thickness of the coating layer is 2-200 nm.
Carbonaceous coating or organic polymer coating can increase the electron conductance of material, and the coating structure can prevent that electrolyte and active material direct contact from producing too much surface side reaction simultaneously, reduces the loss of lithium ion in irreversible capacity and the battery, and in addition, the coating can play certain inhibitory action to the material at the expansion and contraction of charge-discharge in-process, synthesizes the effect that plays the cyclicity ability of promotion battery.
Drawings
Fig. 1 is a diagram showing a structure of a battery using a silicon-oxygen composite negative electrode material according to an embodiment of the present invention.
Fig. 2 is a schematic structural view of an oxygen composite anode material according to a first embodiment of the present invention.
Fig. 3 is a diagram illustrating the distribution of the mass concentration of the components of the silicon-oxygen composite negative electrode material according to the first embodiment of the present invention.
Fig. 4 is a sectional electron microscope image of a sample of the silicon-oxygen composite negative electrode material according to the first embodiment of the present invention.
Fig. 5 is a schematic view of a porous structure of a silicon-oxygen composite negative electrode material according to a second embodiment of the present invention.
Fig. 6 is a flow chart of a manufacturing process of the silicon-oxygen composite negative electrode material according to the embodiment of the present invention.
Fig. 7 is a surface electron microscope image of a silicon-oxygen composite negative electrode material according to a second embodiment of the present invention.
Fig. 8 is a graph of cycle data for batteries fabricated by testing the silicon oxygen composite anode materials of the respective examples.
Detailed Description
The embodiments of the present invention will be described below with reference to the drawings.
The embodiment of the invention mainly relates to a novel silica composite anode material, which is used for manufacturing an anode of a lithium battery. The lithium battery is mainly used for terminal consumer products, such as various mobile phones, tablet computers, notebook computers and other wearable or movable electronic equipment.
As shown in fig. 1, 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 anode and cathode materials can release and insert lithium ions to realize energy storage and release, the electrolyte is a carrier for transmitting the lithium ions between the anode and the cathode, and the diaphragm can penetrate the lithium ions but is not conductive so as to separate the anode and the cathode to prevent short circuit. The positive composite negative electrode material generally plays a decisive role in key performance factors such as the energy storage function of a lithium battery, the energy density, the cycle performance and the safety of a battery core of the lithium battery, and the like.
The negative electrode material provided by the embodiment of the invention is a silicon oxide composite negative electrode material with high gram specific capacity (mAh/g). The lithium silicate formed by doping lithium changes the crystal structure of the material and reduces irreversible reaction, so that the first effect of the silicon oxide material is improved on the basis of keeping higher gram specific capacity of the silicon oxide material, and the aim of improving the energy density of a battery cell is fulfilled.
Meanwhile, through the gradient structure design of the inner core and the silicate, the pH value of the composite negative electrode material can be reduced, the composite negative electrode material can keep better processing performance, and the electrochemical performance and the processing stability of the material can be considered at the same time. In addition, the surface of the composite negative electrode material provided by the embodiment of the invention is provided with a radial taper hole structure, so that the volume expansion of the material in the charging and discharging process can be relieved, more abundant lithium ion transmission channels can be provided, the improvement of the long cycle life of the battery is facilitated, and the overall competitiveness of the product is improved.
Materials examples
As shown in fig. 2, the silicon-oxygen composite negative electrode material according to the first embodiment of the present invention includes an inner core 1, a coating layer 3 coated outside the inner core 1, and an intermediate layer 2 located between the inner core 1 and the coating layer 3.
The core 1 is a lithium-doped silica core, wherein the lithium-doped silica core is a mixture of a plurality of materials. The inner core 1 comprises a mixture of nano silicon (nano Si), silicon oxide and lithium silicate, wherein the particle radius r of the mixture is 50 nm-20 um.
The chemical formula of the silicon oxide is SiO x Wherein x is more than or equal to 0.6 and less than or equal to 2, wherein x is the chemical formula SiO x Independent variables, which are not related to x of other chemical formulas. The subscript variables used in the following formulas to indicate the molecular ratio are also identical to the principle of x, and the same letters in different formulas such as x, y, etc. are not related but are not distinguished for convenience of description. As shown in fig. 3, the mass content ratio distribution of the silicon oxide in the entire core increases from the coating layer 3 to the radial direction of the core 2, wherein the outer shell in fig. 3 refers to the coating layer 3. The increase may be a gradient increase, for example, it may mean that the mass ratio on the circumference having the same distance from the center of the silicon oxide anode material is the same, and the increase gradually or stepwise changes with the distance from the center of the anode material.
The chemical formula of the lithium silicate is Li 2x Si y O (x+2y) Is the product formed after the reaction of lithium doped silica, is a mixture of various silicates, the composition of which includes but is not limited to Li 4 SiO 4 、Li 2 SiO 3 And Li 2 Si 2 O 5 And the like. The mass content of the lithium silicate in the core 1 is distributed in a manner that the coating layer 3 is gradually reduced towards the core 1, namely the mass ratio of the lithium silicate on the outermost layer of the core 1 is the highest, and then the lithium silicate is gradually reduced towards the center of the core 1.
In addition, the inner core 1 and the intermediate layer 2 further include non-metal doping elements such as C, H, N, B, P, S, Cl and F, and the non-metal doping elements are distributed in the inner core 1 in a gradient manner, wherein the gradient distribution is gradually decreased from the outside of the intermediate layer 2 to the center of the inner core 1.
The non-metal elements C, H, N, B, P, S, Cl and F are present in the mixture of the inner core 1 and the intermediate layer 2 in a doped form, and the molar ratio of the doping element to the substance to be doped is less than 5%.
The gradient distribution is that according to a diffusion principle, the addition amount and the synthesis temperature of a lithium source are controlled when the inner core 1 is manufactured, and the concentration of the lithium source in the material decreases in a gradient manner from outside to inside, so that the content of nano silicon and silicate in the inner core 1 decreases from outside to inside, and the content of silicon oxide increases from outside to inside. The core structure formed by gradient distribution can prevent the content of nano silicon generated by doping reaction in the material core from being too high, effectively reduce the stress born by the core in the charge and discharge process and avoid the core from being broken due to long-time circulation. In addition, the lithium doping component of the silicon-oxygen composite negative electrode material is mainly contained in lithium silicate and nano lithium, and the mass content in the inner core 1 is reduced in a gradient manner from the coating layer 3 to the inner core 1, namely the mass ratio of the lithium doping element component at the outermost layer of the inner core 1 is highest, and then the lithium doping component is reduced layer by layer towards 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 generated by introducing non-lithium metal salt into the surface of the inner core 1 and reacting. The intermediate layer 2 includes non-lithium silicate, which means a doped metal silicate other than lithium silicate, nano silicon, silicon oxide, and lithium silicate. The non-lithium silicate has the chemical formula M x Si y O z Wherein, the M comprises one or more of Al, Ca, Mg, Be, Sr, Ba, Ti and other metal elements. As shown in fig. 3, the mass ratio of the non-lithium silicate in the intermediate layer 2 decreases in a gradient manner from the coating layer 3 to the core 1, that is, the mass ratio of the non-lithium silicate at the outermost layer of the intermediate layer 2 is the highest, and then the mass ratio of the non-lithium silicate closer to the center of the core 1 is lower in the entire intermediate layer 2, wherein the outer shell shown in the figure refers to the coating layer 3. The concentration distributions of the M element and the non-lithium silicate are consistent. The non-lithium silicate is generated in situ on the outer layer of the inner core 1, has a compact structure which is not water-soluble or non-alkaline or alkalescent, can effectively relieve the dissolution of the internal water-soluble lithium silicate, and reduces the pH value of the silicon-oxygen composite negative electrode material. The intermediate layer 2 also comprises silicon oxide of the formula SiO x Wherein x is more than or equal to 0.6 and less than or equal to 2, wherein x is the chemical formula SiO x Independent variables, the silica mass content distribution is the opposite of the non-lithium silicate. The mass content of the silicon oxide in the intermediate layer 2 is distributedThe mass ratio of the non-lithium silicate at the outermost layer of the intermediate layer 2 is the least, and then the mass ratio of the non-lithium silicate at the central position of the inner core 1 is higher in the whole intermediate layer 2. The intermediate layer also includes a mixture of nano-silicon, silicon oxide, and lithium silicate.
FIG. 4 shows a sectional secondary electron image of the silicon-oxygen composite anode material sample and the element Mg (M) x Si y O z When M is Mg), the structural distribution inside the sample can be observed in the sectional view, wherein fig. 4 is an electron microscope image mainly used for observing the surface micro-topography or the surface element distribution by using secondary electron imaging and doubly-dispersed electron imaging. The section of the sample is obviously distinguished by dark light gray, and the light gray part is non-lithium silicate Mg formed on part of the lithium-doped silicon oxide surface in situ 2 SiO 4 In fig. 4, the distribution of the corresponding visible Mg element is in agreement with the outline of the left part, and as can be seen from the right part, the concentration of Mg is in a gradient distribution decreasing from the outer layer to the inner core region.
The coating layer 3 is not an essential component of the silicon-oxygen composite negative electrode material in the embodiment of the present invention, and the coating layer 3 may be absent in some embodiments. In some embodiments, the coating layer 3 is a carbonaceous material, a coating layer structure is formed on the outermost layer of the silicon-oxygen composite negative electrode material, and the thickness of the coating layer can be 2-1000 nm. The carbonaceous material is amorphous carbon formed by cracking a carbon source, or a mixture of the amorphous carbon and carbon nanotubes or/and graphene embedded in the amorphous carbon. The coating layer 3 can be a carbonaceous material and/or an organic polymer coating layer, the carbonaceous material coating layer can increase the electronic conductance of the material, and meanwhile, the coating layer structure can prevent electrolyte from being in direct contact with an active material to generate excessive surface side reaction, so that the irreversible capacity and the loss of lithium ions in the battery are reduced.
As shown in fig. 5, in the silicon-oxygen composite anode material according to the second embodiment of the present invention, a porous structure is further disposed on the inner core 1 and the intermediate layer 2. A plurality of pore channels 12 are arranged on the silicon-oxygen composite negative electrode material, soThe pore channels 12 extend from the surface of the intermediate layer 2 from outside to inside, and the pore channels 12 are in a tapered pore shape, and the pore diameter of the pore channels 12 gradually decreases from the surface of the intermediate layer 2 to the center of the inner core 1, that is, the pore diameter gradually decreases in a direction from the surface of the intermediate layer 2 to the inside of the inner core 1. For example, the pore diameter of the opening of the pore channel 12 at the surface of the intermediate layer 2 is larger than the pore diameter of the part located at the inner core 1, that is, D out >D in And the depth of the channels 12 is less than the particle radius r, i.e. D, of the mixture of the core 1 depth <r, and 10nm<D depth <500nm。
In some embodiments, the openings of the channels 12 are uniformly distributed on the surface of the intermediate layer 2, and each channel 12 extends along the surface of the intermediate layer 2 in a radial direction towards the center of the inner core 1.
Because the gradient lithium-doped silicon oxide of the inner core 1 has the structural characteristics that the doping concentration is gradually reduced from the surface to the axis direction of the particles, the distribution of nano Si particles on the surface of the inner core 1 is the most, the expansion of the outer layer of the high-efficiency silicon oxide particles in the charging and discharging process can be relieved by the design of the porous channel structures derived from the middle layer 2 and the surface of the inner core 1 to the axis direction, a complete communication structure is not formed between the pore channel 12 and the pore channel 12, and the structural collapse and performance attenuation caused by excessive side reactions in the electrolyte and the material due to the fact that the pore channel 12 is too deep can be prevented. In addition, the porous channel structure provides more lithium ion diffusion channels, and the quick charge capacity of the material can be improved.
In the third embodiment of the present invention, the coating layer 3 includes a polymer coating layer formed by organic polymerization or polymer dispersion coating.
In the fourth embodiment of the present invention, the polymer coating layer 3 not only coats the surface of the middle layer 2, but also completely fills all the cell channels 12 of the core 1 and the middle layer 2. In some embodiments, the cladding 3 only fills a portion of the channels 12.
In the fifth embodiment of the present invention, the polymer coating layer 3 is directly coated on the surface of the inner core 1, and completely fills all the cell channels 12 of the inner core 1. In some embodiments, the cladding 3 only fills a portion of the cell channels 12.
Second, method embodiment
As shown in fig. 6, a method embodiment of the present invention provides a method for manufacturing a silicon-oxygen composite negative electrode material in a first embodiment. The manufacturing method mainly comprises the following steps:
In particular, silicon oxide and a lithium source are uniformly mixed according to a certain proportion and then transferred into a sagger (n is more than or equal to 0.1) Li /n Si N is less than or equal to 1.0, n is Li /n Si Is the mole ratio between lithium ions and silicon oxide), and then transferring the sagger into a high-temperature furnace in an inert atmosphere or a reducing atmosphere for roasting reaction, wherein the roasting temperature is within the temperature range of 300-900 ℃, and partial lithium-doped silicon oxide, namely the mixture of lithium silicate and silicon oxide, can be obtained. The lithium source used for lithiation doping is lithium salt, and the lithium salt mainly comprises LiH and LiAlH 4 、Li 2 CO 3 、LiNO 3 One or more of LiAc, and LiOH.
The method comprises the following steps of uniformly mixing part of lithiated and doped silicon oxide and non-lithium metal or metal salt according to a certain proportion to obtain a mixture, transferring the mixture into a sagger, putting the sagger into a high-temperature furnace in an inert atmosphere or a reducing atmosphere, roasting at the temperature of 400-1000 ℃, and generating non-lithium silicate on the surface of part of lithium-doped silicon oxide or porous part of lithium-doped silicon oxide in situ to obtain a lithium-doped silicon oxide composite material with a layered structure and gradient distribution, wherein the layered structure refers to the structure of the lithium-doped silicon oxide composite material comprising the inner core 1 and the intermediate layer 2 in one embodiment.
The structural formula of the non-lithium silicate is M x Si y O z M includes but is not limited to Al, Ca,One or more of metal elements such as Mg, Be, Sr, Ba, Ti, Zr and the like, wherein M also comprises but is not limited to simple substance metal or metal salt of the metal elements, and the molar ratio of the metal elements M to Si satisfies 0.01 ≦ n M /n Si ≤0.3。
Specifically, the lithium-doped silicon oxide composite material synthesized in the step 2 is placed in an inert atmosphere furnace, organic carbon source gas is introduced, and a carbon source is subjected to cracking reaction at the temperature of 400-1100 ℃, so that a carbonaceous coating layer is formed on the surface of the lithium-doped silicon oxide composite material.
The step of coating the carbonaceous material includes, but is not limited to, the cracking reaction of the above-mentioned gaseous organic carbon source, solid-phase mixed carbon source coating, pitch coating, hydrothermal reaction coating, oil bath coating, and the like, and may also be resin, sugar, grease, organic acid ester, small molecular alcohol, carbon nanotube, graphene, and the like, but the carbon source is other than the gaseous organic carbon source. The thickness of the coating layer is 2-1000 nm.
Another embodiment of the present invention provides a method for manufacturing the porous silicon-oxygen composite negative electrode material in the second embodiment. The manufacturing method mainly comprises the following steps:
mixing silicon oxide SiOx (x is 1) with the surface carbon coating amount of 4.3% and the average particle size of 5 mu m and lithium hydride LiH serving as a lithium source according to the mass ratio of 100 (8-10) to obtain a mixture, wherein the mixture needs to be mixed for at least 20min in an argon atmosphere by a mixer to ensure that a sample is uniform;
and transferring the mixture into a sagger, transferring the sagger into an atmosphere furnace, introducing argon, reacting at the temperature of 700-800 ℃ for 2 hours, cooling to room temperature, and taking out the sagger to obtain a part of lithium-doped silicon oxide material.
taking 500g of the part of the lithium-doped silicon oxide material prepared in the step 1, adding 1L of 0.2M NaOH aqueous solution, stirring and dispersing at the rotating speed of 500r/min for 1h to obtain a mixed material, and performing pore-forming etching on the mixed material; after the treatment, carrying out suction filtration on the mixed material, taking down a filter cake after the suction filtration is finished, adding 1L of water into the filter cake, stirring and dispersing for 1h at the rotating speed of 500r/min, and then carrying out suction filtration; unreacted NaOH and reaction byproducts are washed away by water, and lithium silicate in the remaining part of the lithium-doped silicon oxide is partially dissolved to form a pore channel structure.
And repeating the operation of performing suction filtration, adding water and suction filtration on the mixed material for 3 times, taking out the filter cake, baking in a incubator at 100 ℃ until the filter cake is dried, and obtaining the partial lithium-doped silicon oxide with the porous structure.
As shown in fig. 7, a surface electron microscope image of the material is shown, and arrows in the figure indicate that the surface of the material is etched and dipped in the present embodiment, and a porous channel structure is formed on the surface of the particles.
uniformly mixing part of the lithium-doped silicon oxide with the porous structure prepared in the step 2 and metal Mg powder at a high speed according to the mass ratio of 100:5, roasting for 1.5h at 850 ℃ in an argon atmosphere, cooling to room temperature, and taking out to obtain the non-lithium silicate Mg formed in situ on the surface of the material 2 SiO 4 Is doped with lithium.
Step 4, manufacturing a carbon material coating layer:
placing the lithium-doped silicon oxide with the gradient structure prepared in the step 3 into an atmosphere furnace, and introducing N 2 Removing residual air in the furnace to ensure that the atmosphere in the furnace is inert atmosphere, raising the temperature of the furnace to 850 ℃, and introducing a carbon source C 2 H 2 Stopping introducing carbon source gas after reacting for 1h, finally cooling to room temperature in inert atmosphere, opening a hearth, and taking out the porous silica composite negativeA pole material.
Step 5 can also be included in some embodiments of the present application for fabricating the silicon oxygen composite anode material into a secondary battery.
Step 5, preparing a secondary battery:
the prepared silicon-oxygen composite negative electrode material is mixed with commercial graphite G49 to form a negative electrode material of 600mAh/G, and the negative electrode material, a conductive agent Super P, a binder SBR and CMC are dispersed in deionized water according to a mass ratio of 95:0.3:3.2:1.5, and are stirred uniformly to obtain electrode slurry; coating the surface of the copper foil, and drying at 85 ℃ to obtain a negative electrode plate; and matching with a commercial lithium cobaltate positive electrode material, wherein the electrolyte is 1mol/L LiPF6/EC + PC + DEC + EMC (the volume ratio is 1:0.3:1:1), the diaphragm is a PP/PE/PP three-layer diaphragm, the thickness is 10 mu m, and the soft package battery with the thickness of about 3.7Ah is manufactured. The pouch cell can be used to test the full cell performance of the material.
In some method embodiments of the present invention, a method for manufacturing the silicon-oxygen composite anode material in the third embodiment is provided, where the coating layer 3 of the silicon-oxygen composite anode material includes a coating layer formed by organic polymerization or polymer dispersion coating.
The manufacturing method of the high-molecular polymer coating layer comprises the following steps: dispersing 100g of the product obtained in the step 2 in the first embodiment in 300g of a xylene solvent, adding 2g of uncured epoxy resin particles, stirring for 3 hours at 60 ℃, then ultrasonically dispersing for 60 minutes, adding 0.5g of a T31 curing agent, stirring for 2 hours, and spray-drying at 100 ℃ to obtain the polymer organic matter-coated gradient-structure lithium-doped silicon oxide material.
In some method embodiments of the present invention, a method for manufacturing the silicon-oxygen composite anode material in the fourth embodiment is provided, in which the polymer coating layer 3 of the silicon-oxygen composite anode material not only coats the surface of the intermediate layer 2, but also permeates and fills all the pore channels of the inner core 1 and the intermediate layer 2.
The manufacturing method of the high-molecular polymer coating layer comprises the following steps: and (3) dispersing 100g of the product obtained in the step 3 in the second embodiment in 300g of a xylene solvent, adding 5g of uncured epoxy resin particles, stirring for 6 hours at 60 ℃, performing ultrasonic dispersion for 60 minutes, adding 2g of a T31 curing agent, stirring for 2 hours, and performing spray drying at 100 ℃ to obtain the high-molecular polymer coated gradient-structure lithium-doped silicon oxide material.
In some method embodiments of the present invention, a manufacturing method of the silicon-oxygen composite anode material in the fifth embodiment is further provided, where the coating layer 3 of the silicon-oxygen composite anode material is directly coated on the surface of the inner core 1, and also completely fills part or all of the pore channels of the inner core 1.
The manufacturing method of the polymer coating layer comprises the following steps: cetyl trimethyl ammonium bromide (CTAB, (C16H33) N (CH3)3Br, 7.3g) is dissolved in HCl (500mL) solution at the temperature of 0-4 ℃, 100g of the product lithium doped silica obtained in the step 1 in the first embodiment is added, then Pyrrole monomer (Pyrrole, 8.3mL) is added, the mixture is subjected to ultra-dispersion for 30 minutes and then stirred for 2 hours, then ammonium persulfate (APS, 13.7g and dissolved in 100mL of 1mol/L hydrochloric acid) solution is added dropwise, the stirring state is kept, the mixture is subjected to heat preservation reaction at the temperature of 0-4 ℃ for 24 hours and then filtered, the obtained grey green precipitate is washed with 1mol/L HCl solution for three times and then washed with purified water until the solution is colorless and neutral, and then the precipitate is dried at the temperature of 80 ℃ for 24 hours, so that the gradient structure lithium doped silica material coated by the high molecular polymer can be obtained.
The silicon-oxygen composite negative electrode material (Mg-Li doped SiOx) having a gradient structure in the first embodiment, the silicon-oxygen composite negative electrode material (Porous Mg-Li doped SiOx) having a Porous structure in the second embodiment, the silicon-oxygen composite negative electrode material (Poly Mg-Li doped SiOx) having an organic coating layer in the third embodiment, and the silicon-oxygen composite negative electrode material (Poly2 Mg-Li doped SiO) having an organic coating layer in the fourth embodiment x ) The silicon-oxygen composite negative electrode material (Poly Li doped SiO) with the organic coating layer in the fifth embodiment x ) And comparing the physical and chemical parameters of the common non-porous and non-gradient structure partial lithium doped silicon oxide material (Li doped SiOx) with the following table 1:
TABLE 1 comparison of the basic characteristics of all examples
Therefore, the performance of the silica composite anode material with the gradient structure in the first embodiment, the silica composite anode material with the porous structure in the second embodiment, and the silica composite anode material with the organic coating layer in the third embodiment are both significantly improved compared with the performance of a common lithium-doped silicon oxide material without a pore channel and a gradient structure, and particularly have significant advantages in processing performance, half-electrode sheet expansion rate and 500-cycle retention rate, and specific analysis is as follows:
1. the lithium-doped silicon oxide with the gradient structure of the silicon-oxygen composite negative electrode material in the first embodiment forms a non-water-soluble or non-alkaline or weakly alkaline non-lithium silicate layer in situ on the basis of the original lithium-doped silicon oxide material. On one hand, the non-lithium silicate layer is alkalescent, on the other hand, the composite layer can relieve the dissolution of water-soluble strong-alkaline lithium silicate in the lithium-doped silicon oxide material in water, so that the slow release effect is achieved, the pH value of the material is effectively reduced, the slurry processing performance of the negative electrode material is reflected, and the problems of gas generation, easy material falling during coating and the like of the traditional lithium-doped silicon oxide slurry are well solved.
2. In the second embodiment, the porous channel and the gradient-structure lithium-doped silicon oxide of the silicon-oxygen composite cathode material are etched and impregnated before the gradient-structure material is synthesized to manufacture the radial horn hole, water-soluble lithium silicate with a certain depth on the surface of the silicon oxide can be removed in the pore-forming process, and the in-situ construction of the non-lithium silicate gradient structure is performed on the basis, so that the effect of reducing the pH value can be better achieved. Meanwhile, the porous channel structure can effectively relieve stress generated by the expansion of the silicon-based material on the outer layer of the silicon oxide and ensure the integrity of the structure. From the experimental data in Table 1, it can be seen that the half-electrode sheet expansion rate of Porous Mg-Li processed SiOx (example two) is 21%, which is significantly reduced compared to examples one and three. Besides the beneficial effects, the multi-pore channel structure can improve the retention amount of electrolyte in the material, provide rich lithium ion diffusion channels, promote lithium ion transmission and improve the multiplying power performance of the battery cell.
3. The polymer coating layer formed on the material surface of the silicon-oxygen composite negative electrode material in the third embodiment can prevent the strong-basicity lithium silicate and/or residual lithium in the inner core from being dissolved in water in the slurry preparation process, so that the effects of reducing the water-soluble pH value of the material and increasing the stability of the slurry are achieved, and the polymer coating layer is uniformly coated on the material surface and has a certain inhibiting effect on the volume expansion of the material in the charging and discharging processes.
4. The polymer coating layers formed on the material surface and in the pore channels of the silicon-oxygen composite negative electrode material in the fourth embodiment can prevent the strong-basicity lithium silicate and/or residual lithium in the inner core from being dissolved in water in the preparation process of the slurry, so that the water-soluble pH value of the material is reduced, the stability of the slurry is improved, and the polymer also permeates and fills all the pore channels of the inner core 1 and the middle layer 2, so that the volume expansion of the material in the charging and discharging processes is inhibited to a certain extent.
5. In the fifth embodiment, the polymerization reaction of the silicon-oxygen composite negative electrode material occurs in a hydrochloric acid solution, the hydrochloric acid can completely dissolve the alkaline water-soluble components in the lithium-doped silicon oxide, the pH value of the material is effectively reduced, the mass ratio of active material silicon crystal particles is increased after the alkaline components are dissolved, the formed pore channels can be automatically filled with organic small molecule reactants, and after a polymerization reaction initiator is added, the generated polymer can be uniformly coated on the surface of the material and can fill the pore channels, so that the volume change of the material in the charging and discharging process can be effectively buffered. The high-molecular polypyrrole generated in the embodiment also has the conductivity and lithium storage activity, and plays a certain role in improving the electrical property of the doped silicon oxide.
As shown in the battery cycle data corresponding to the standard battery cell tested in fig. 8, capacity retention rates of the lithium ion battery prepared by using the materials in the first, second, and third examples and the common non-porous and non-gradient structure partial lithium-doped silicon oxide material after 500 cycles are respectively 76%, 90%, and 66%, cycle performance of the battery cell prepared by using the gradient structure lithium-doped silicon oxide material in the first, second, and third examples is significantly better than that of the battery cell of the untreated lithium-doped silicon oxide in the sixth example, and cycle performance of the battery cell is the most excellent after the second, and third examples are respectively coated with the porous structure and the polymer of the present invention. In principle, the lithium-doped silicon oxide material has better processing performance, lower material expansion, stronger structural stability, lower surface side reaction and less lithium ion consumption caused by structural damage after the design of the non-lithium silicate in-situ formed gradient structure and the porous channel structure, and finally brings the comprehensive improvement effect of the cycle performance. In addition, the polymer coating has a good slurry stabilizing effect, the expansion of the pole piece is effectively inhibited, and the cycle performance of the battery cell is improved.
It is clear to those skilled in the art that, for convenience and brevity of description, the specific working processes of the above-described systems, apparatuses and units may refer to the corresponding processes in the foregoing method embodiments, and are not described herein again.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (20)
1. The silicon-oxygen composite negative electrode material is characterized by comprising an inner core, a coating layer and an intermediate layer positioned between the inner core and the coating layer;
the intermediate layer comprises a non-lithium silicate, and the mass content proportion distribution of the non-lithium silicate in the intermediate layer is decreased from the intermediate layer to the inner core;
the inner core and the middle layer are provided with a plurality of pore channels, the pore channels extend from the surface of the middle layer to the inner core direction, and the pore diameters of the pore channels are gradually reduced from the surface of the middle layer to the center direction of the inner core.
2. The silicon oxygen composite anode material of claim 1, wherein the non-lithium silicate comprises a metal element M comprising a combination of one or more of Al, Ca, Mg, Be, Sr, Ba, Ti, Zr.
3. The silicon oxygen composite negative electrode material according to claim 2, wherein the molar ratio of the element M to Si in the non-lithium silicate satisfies 0.01. ltoreq. n M /n Si ≤0.3。
4. The silicon-oxygen composite negative electrode material of claim 1, wherein the mass content ratio distribution of the non-lithium silicate in the intermediate layer decreases from the intermediate layer to the inner core comprises a gradient decrease from the intermediate layer to the inner core, wherein the gradient decrease means that the mass ratio on the circumference at the same distance from the center of the inner core is the same, and the mass ratio decreases stepwise as the distance from the center of the inner core decreases.
5. The silicon-oxygen composite negative electrode material as claimed in claim 1, wherein the intermediate layer is a mixture layer formed by introducing a second phase metal salt on the surface of the inner core and reacting to generate the non-lithium silicate in situ on the surface of the inner core.
6. The silicon-oxygen composite anode material of claim 1, wherein the intermediate layer further comprises silicon oxide (SiO) x Wherein x is not less than 0.6 and not more than 2, wherein x is the SiO x The mass content proportion distribution of the silicon oxide in the middle layer is increased from the cladding layer to the inner core.
7. The silicon oxygen composite negative electrode material of any one of claims 1 to 6, wherein the pore channels are tapered.
8. The silicon oxygen composite anode material of claim 1, wherein the inner core and the intermediate layer each comprise a mixture of nano-silicon, silicon oxide, and lithium silicate, the poresDepth D of track depth Less than the particle radius r of the core mixture and 10nm<D depth <500nm。
9. The silicon oxygen composite anode material of claim 8, wherein the particle radius r of the core mixture is 50nm to 20 um.
10. The silicon-oxygen composite anode material as claimed in claim 1, wherein the coating layer covers the surface of the intermediate layer and completely fills all the pore channels.
11. The silicon oxygen composite anode material as claimed in claim 1, wherein the core comprises a mixture of nano silicon, silicon oxide and lithium silicate, the mass content ratio distribution of the silicon oxide in the whole core is increased in a gradient from the cladding layer to the radial direction of the core, the mass content ratio distribution of the lithium silicate in the core is decreased in a gradient from the cladding layer to the radial direction of the core, and the mass content ratio distribution of the nano silicon in the core is decreased in a gradient from the cladding layer to the radial direction of the core.
12. The silicon oxygen composite anode material of claim 11, wherein the inner core further comprises C, H, N, B, P, S, Cl and one or more non-metal doping elements of F, the non-metal doping elements are distributed in the inner core in a gradient manner, and the gradient distribution is gradually decreased from the middle layer to the center of the inner core; the molar ratio of the nonmetal doping elements is less than 5%.
13. The silicon-oxygen composite anode material of claim 1, wherein the carbonaceous material is a mixture of the amorphous carbon alone or the mixture of the amorphous carbon and carbon nanotubes or graphene embedded in the amorphous carbon.
14. The silicon-oxygen composite negative electrode material according to claim 1, wherein the coating layer is a carbonaceous material or comprises a coating layer formed by organic polymerization or polymer dispersion coating.
15. The silicon-oxygen composite negative electrode material as claimed in claim 1, wherein the coating layer has a thickness of 2 to 200 nm.
16. A lithium battery comprising a positive electrode material, an electrolyte, a separator, and the silicon oxygen composite negative electrode material according to any one of claims 1 to 15.
17. A terminal device comprising a charging and discharging circuit and an electric element, characterized by further comprising a lithium battery according to claim 16, wherein the lithium battery is connected to the charging and discharging circuit, and is charged by the charging and discharging circuit or supplies power to the electric element.
18. A method for manufacturing a silicon-oxygen composite anode material comprises the following steps:
step one, uniformly mixing silicon oxide and a lithium source, transferring the mixture into a sagger, and roasting the mixture in an inert atmosphere or a reducing atmosphere to obtain partially lithiated and doped silicon oxide; performing pore-forming etching on the partial lithiation doped silicon oxide to form a multi-pore-channel structure to obtain partial lithiation doped silicon oxide with the multi-pore-channel structure;
step two, uniformly mixing the partial lithiation doped silicon oxide with the porous structure and non-lithium metal, or uniformly mixing the partial lithiation doped silicon oxide with the porous structure and non-lithium metal salt, and then roasting to generate non-lithium silicate on the surface of the partial lithiation doped silicon oxide with the porous structure in situ to obtain a lithium-doped silicon oxide composite material with gradient distribution;
step three, putting the lithium-doped silicon oxide composite material in the gradient distribution into an inert atmosphere furnace, introducing organic carbon source gas, forming a carbonaceous coating layer on the surface of the lithium-doped silicon oxide composite material in the gradient distribution,obtaining a silicon-oxygen composite negative electrode material, wherein the silicon-oxygen composite negative electrode material comprises an inner core, a coating layer and an intermediate layer positioned between the inner core and the coating layer; the intermediate layer comprises a non-lithium silicate, the non-lithium silicate comprises a metal element M, the metal element M comprises one or more of Al, Ca, Mg, Be, Sr, Ba, Ti and Zr, and the mass content proportion distribution of the non-lithium silicate in the intermediate layer is decreased from the intermediate layer to the inner core; the intermediate layer further comprises silicon oxide SiO x Wherein x is not less than 0.6 and not more than 2, wherein x is the SiO x An independent variable; the inner core and the middle layer are provided with a plurality of pore channels, the pore channels extend from the surface of the middle layer to the inner core direction, and the pore diameters of the pore channels are gradually reduced from the surface of the middle layer to the center direction of the inner core.
19. The method for manufacturing the silicon-oxygen composite negative electrode material of claim 18, wherein the lithium source is elemental lithium or lithium salt, and the lithium salt comprises LiH and LiAlH 4 、Li 2 CO 3 、LiNO 3 One or more of LiAc, and LiOH.
20. The method for producing a silicon-oxygen composite anode material according to claim 18 or 19, wherein the molar ratio of the element M to Si in the non-lithium silicate satisfies 0.01. ltoreq. n M /n Si ≤0.3。
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