CN107240677A - A kind of micro-nano structure carbon silicon complex microsphere and its production and use - Google Patents
A kind of micro-nano structure carbon silicon complex microsphere and its production and use Download PDFInfo
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- CN107240677A CN107240677A CN201610183286.0A CN201610183286A CN107240677A CN 107240677 A CN107240677 A CN 107240677A CN 201610183286 A CN201610183286 A CN 201610183286A CN 107240677 A CN107240677 A CN 107240677A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
A kind of micro-nano structure carbon silicon complex microsphere and its production and use.Nano SiO 2 particle and protective agent and carbon nanomaterial are carried out compound and micro nano structure by the present invention by spray drying process; carbon/SiO 2 composite microsphere is made by being heat-treated under nonoxidizing atmosphere; further by metallothermic processes, micro-nano structure carbon silicon complex microsphere is obtained.The preparation method of the present invention is not only with low cost, technique is simple, energy consumption is low, can scale; and the carbon nano silicon particles in gained micro-nano structure carbon silicon complex microsphere have a seed nucleus-hollow shell structure, it is used as lithium ion battery negative material discharge and recharge volume and capacity ratio height, stable circulation.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of micro-nano structure carbon silicon
Complex microsphere and its production and use, more particularly to a kind of micro-nano structure with core-hollow shell structure
Carbon silicon complex microsphere and its production and use.
Background technology
Silicon can be used as a kind of negative electrode active material for replacing graphite in secondary cell, especially lithium ion battery
Material, it has more preferable capacity.However, silicon materials in charge and discharge process with huge Volume Changes,
The mechanical stress of generation causes the disengaging between the efflorescence of active material and structural breakdown and material and collector, from
And cause capacity to decay rapidly and cycle performance of battery reduction.Further, since this Volumetric expansion, silicon
It is difficult to form stable solid electrolyte interface SEI films in the electrolytic solution, causes efficiency for charge-discharge to reduce, plus
The further deterioration of fast cycle performance.By silicon materials are nano-structured and/or porous so with carbon nanometer material
Nano composite material is constructed in material combination can solve silicon to a certain extent in charge and discharge process because volume is swollen
Structure caused by swollen effect and surface and interface instability problem, so as to improve its discharge and recharge, cycle performance.
It is worth noting that, the nano-structured and/or porous of material generally directly results in active electricity
The tap density of pole material is greatly reduced, and seriously constrains the lifting of its volume and capacity ratio and energy density, resistance
Hinder the miniaturization of battery and/or related energy-storage system.Research shows, constructs micro-nano structure SiClx or carbon silicon is compound
Material is a kind of effective way (the High Volumetric Capacity Silicon-Based solved the above problems
Lithium Battery Anodes by Nanoscale System Engineering,Nano Letters 2013,13,
5578；A pomegranate-inspired nanoscale design for large-volume-change lithium
battery anodes,Nature Nanotechnology 2014,9,187)。
However, micro-nano structure SiClx or carbon-silicon composite material rely primarily on the gas such as the monosilane of high risk at present
State silicon source, or expensive solid construction business silica flour or silicon grain or silicon quantum dot or be unfavorable for environment
Hf etching process or harshness (such as, high vacuum, high temperature etc.), power consumption and/or the synthesis of complexity
Journey, material and method seriously restrict the performance performance of such micro-nano structure composite in itself and reality should
With.Therefore find that a kind of technique is simple, energy consumption is low, can scale and method with low cost carry out carbon silicon and answer
The preparation for closing microballoon is current urgent problem to be solved.
Aerosil (gas-phase silica) is one of ultra tiny New Inorganic Materials of extremely important high-tech,
Due to its particle diameter very little, therefore specific surface area is big, and superficial attractive forces are strong, and surface can be big, chemical purity height,
Dispersive property is good, have special performance in terms of thermal resistance, resistance, with its superior stability, reinforcement
Property, thickening property and thixotropy, show unique characteristics in numerous subjects and field, do not replace.
Nano silicon is commonly called as " ultra-fine white carbon black ", is widely used for every profession and trade as additive, catalysis
Agent carrier, petrochemical industry, decolorising agent, delustering agent, rubber reinforcing filler, plastics filler, ink thickening
Agent, the soft buffing compound of metal, insulation and thermal insulation filler, high-grade daily-use cosmetics filler and sprayed on material, doctor
The various fields such as medicine, environmental protection, and provide new material basis and technology guarantor for the development of related industrial fields
Card.Due to industrializing the progress of mass production techniques so that aerosil is with low cost, is expected into
For the important raw and processed materials of nano silicon material, it is used widely in energy storage field.But, directly utilize nanometer
Silica prepares silicon materials by metallothermic reduction easily to be occurred to bond and forms that size is larger, structure is mixed and disorderly
Silicon materials, do not simply fail to improve material tap density and volume and capacity ratio, also serious restriction material circulation is steady
Qualitatively lifted.
The B of CN 103531760 disclose a kind of yolk-eggshell structural porous silicon-carbon complex microsphere and its preparation side
Method.It comprises the following steps：(1) it is dispersed in water using silica, three hydroxyl first is added under stirring condition
Then base aminomethane, regulation pH value is proportionally added into polyethylene glycol propane diols-polyethylene glycol to 8~9
And dopamine, stirring, centrifuge, wash and simultaneously dry, obtain the precipitation of poly-dopamine coated silica, then
A period of time is heated under nitrogen protection atmosphere, the black powder of porous coated silica is obtained；(2) put
In the certain density NaOH aqueous solution, a period of time is soaked under water bath condition, centrifuges, wash and do
It is dry, obtain the porous carbon coated silica@Void@mpC powders of yolk-eggshell structure；(3) by step
(2) the porous carbon coated silica@Void@mpC powders obtained are mixed with magnesium powder by a certain percentage, argon
Magnesiothermic reduction reaction is carried out under gas atmosphere, is then 1 by solid-to-liquid ratio by the powder after magnesium heat：200~1：100
It is placed in the HCl/water solution that concentration is 1~2mol/L, soaks 12~24h, centrifuge, separate and wash removal
HCl, is then placed in the HF solution that mass concentration is 5~10%, soaks 0.5~1.5 hour, centrifugation point
From washing removes HF, dries, that is, the silicon-carbon for obtaining the coated porous silicon of porous carbon of yolk-eggshell structure is answered
Close microballoon.But, the preparation method process is cumbersome, and condition is harsh, and needs to perform etching using HF,
HF can be polluted to environment, be unfavorable for industrialization promotion.
The content of the invention
Above mentioned problem for preparing carbon-silicon composite material presence in the prior art, it is an object of the invention to carry
It is particularly a kind of that there is core-hollow for a kind of micro-nano structure carbon silicon complex microsphere and its preparation method and application
Micro-nano structure carbon silicon complex microsphere of shell structure and its production and use.
To reach this goal of the invention, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of preparation method of micro-nano structure carbon silicon complex microsphere, it is described
Method comprises the following steps：
Using silica dioxide granule and protectant mixed solution as the precursor solution of spray drying, sprayed
Mist is dried and is heat-treated, and is prepared micro-nano structure carbon/SiO 2 composite microsphere, then, is passed through metal
Thermal reduction prepares micro-nano structure carbon silicon complex microsphere.
In the present invention, described protective agent is glucose, sucrose, fructose, maltose, chitosan, lemon
Acid, urea, ascorbic acid, starch, protein, gelatin, Arabic gum, alginate, cellulose,
Phenolic resin, polyvinylidene fluoride, polyaminoacid, polyvinylpyrrolidone, poly- carbon ester, polyvinyl alcohol,
Polyethylene glycol, polymethyl methacrylate, polyethyl methacrylate, polyacrylic resin, polychlorostyrene second
In alkene, polyacrylonitrile, PLA or polystyrene any one or at least two mixture.
Protectant mixture typical case of the present invention but non-limiting examples have the mixing of dextrose and saccharose
The mixture of the mixture of thing, glucose and gelatin, maltose and polyvinylpyrrolidone, ascorbic acid and
The mixture of poly- carbon ester, the mixture of urea, protein and chitosan, citric acid, starch, cellulose and
Mixture of polyethyl methacrylate etc..
Preferably, the silica dioxide granule is aerosil particle.
Preferably, the particle diameter of the silica dioxide granule be 5nm-300nm, for example can for 5nm, 10nm,
20nm, 50nm, 100nm, 150nm, 200nm, 250nm or 300nm etc..
Preferably, in the precursor solution of the spray drying, solvent is water and/or organic solvent.
Preferably, in the precursor solution of the spray drying, the mass concentration of solute is 0.1%-60%, example
Such as can for 0.1%, 1%, 3%, 4%, 5%, 6%, 8%, 10%, 12%, 15%, 17%, 19%,
20%th, 23%, 25%, 30%, 33%, 35%, 40%, 42%, 45%, 50%, 55% or 60%
Deng preferably 15%.
Preferably, the silica and protectant mass ratio are 1:(0.1-50), for example, can be 1:0.5、
1:1、1:3、1:10、1:15、1:20、1:30、1:40 or 1:50 etc..
As the optimal technical scheme of the method for the invention, also wrapped in the precursor solution of the spray drying
Containing carbon nanomaterial.
Preferably, the carbon nanomaterial is CNT, graphene, graphene oxide, the stone of reduction
It is any one in black olefinic oxide, carbon fiber, bacteria cellulose based carbon fiber or bacteria cellulose class carbon cilium
Kind or at least two mixture.The mixture of the carbon nanomaterial is typical but non-limiting examples have：Carbon
The mixture of the mixture of nanotube and graphene, CNT and graphene oxide, graphene and carbon are fine
Mixture of dimension etc..
Preferably, the charging rate of the spray drying is 0.5mL/min-100mL/min, for example, can be
0.5mL/min、2mL/min、5mL/min、8mL/min、10mL/min、15mL/min、
18mL/min、20mL/min、22mL/min、25mL/min、30mL/min、32mL/min、
34mL/min、36mL/min、40mL/min、45mL/min、50mL/min、53mL/min、
55mL/min, 60mL/min, 65mL/min, 70mL/min, 80mL/min, 90mL/min or
100mL/min etc., preferably 10mL/min-60mL/min.
Preferably, the EAT of the spray drying be 100 DEG C -300 DEG C, for example can for 100 DEG C,
110℃、120℃、130℃、150℃、160℃、170℃、180℃、190℃、200℃、
215 DEG C, 220 DEG C, 230 DEG C, 250 DEG C, 280 DEG C or 300 DEG C etc., preferably 120 DEG C -220 DEG C.
Preferably, the leaving air temp of the spray drying is automatically adjusted by equipment.
Preferably, the carrier gas of the spray drying is air or inert gas.
Preferably, in the spray drying, the precursor solution of spray drying is atomized into using atomizer
Drop, the atomizer is power formula atomizer, pneumatic atomizer, rotary atomizer or ultrasonic ultrasonic delay line memory
In any one.
In the present invention, when the precursor solution of spray drying is silica dioxide granule and protectant mixed solution
When, the solvent of the precursor solution is volatilized in being heated in hothouse using the precursor solution of spray drying,
Directly obtain by nano SiO 2 particle and protective agent micron order solid powder；When the presoma of spray drying
When solution is the mixed solution of silica dioxide granule, protective agent and carbon nanomaterial, before spray drying
Drive liquid solution makes the solvent of the precursor solution volatilize in being heated in hothouse, directly obtains and is received by silica
The micron order solid powder of rice grain, protective agent and carbon nanomaterial.
Heat treatment of the present invention is carried out under the conditions of nonoxidizing atmosphere.
Preferably, the nonoxidizing atmosphere is in helium atmosphere, neon atmosphere, argon gas atmosphere or hydrogen atmosphere
Any one or at least two combination, more preferably argon gas atmosphere and/or hydrogen atmosphere.
" argon gas atmosphere and/or hydrogen atmosphere " of the present invention refers to：Can be argon gas atmosphere or hydrogen
Gas atmosphere, can also be the mixed atmosphere being made up of the gaseous mixture of argon gas and hydrogen.
Preferably, the temperature of the heat treatment be 300 DEG C -1000 DEG C, for example can for 300 DEG C, 320 DEG C,
350℃、380℃、400℃、420℃、450℃、500℃、550℃、600℃、700℃、
800 DEG C, 880 DEG C, 900 DEG C or 1000 DEG C, preferably 400 DEG C -900 DEG C.
Preferably, the heat treatment time be 30min-24h, for example can for 30min, 40min, 50min,
1h, 2h, 3h, 5h, 7h, 8h, 9h, 10h, 11h or 12h etc., preferably 2h-12h.
In the present invention, through Overheating Treatment, protective agent occurs carbonization and/or is denatured, and changes into carbon hollow shell, from
And prepare micro-nano structure carbon/SiO 2 composite microsphere.
In the method for the invention, when spray drying precursor solution for silica dioxide granule with it is protectant
During mixed solution, after spray drying and heat treatment, obtain micro-nano structure carbon/silica be combined it is micro-
Ball；When the precursor solution of spray drying is molten for the mixing of silica dioxide granule, protective agent and carbon nanomaterial
During liquid, after spray drying and heat treatment, obtain micro-nano structure carbon/SiO 2 composite microsphere and received with carbon
The mixture of rice material.
Metallothermic processes of the present invention prepares micro-nano structure carbon silicon complex microsphere process：By micro-nano knot
Structure carbon/SiO 2 composite microsphere is mixed with reducing agent, and 100 DEG C -1200 DEG C are warming up under an inert atmosphere,
0.5h-60h is reduced, room temperature is cooled to, with drying is washed after acid soak, micro-nano structure carbon silicon is obtained and is combined
Microballoon.
During metallothermic reduction of the present invention, the temperature of heating is 100 DEG C -1200 DEG C, for example, can be
100℃、200℃、250℃、350℃、500℃、600℃、700℃、800℃、900℃、
1000 DEG C, 1100 DEG C or 1200 DEG C etc..
During metallothermic reduction of the present invention, time of reduction is 0.5h-60h, for example can for 0.5h,
3h、5h、10h、15h、20h、25h、28h、30h、33h、35h、37h、40h、45h、48h、
50h, 55h or 60h etc..
Preferably, the mass ratio of the micro-nano structure carbon/SiO 2 composite microsphere and reducing agent is 1:
(0.1-50), such as 1:0.1、1:1、1:2、1:3、1；5、1:7、1:10、1:13、1:15、1:18、
1:20、1:25、1:28、1:30、1:33、1:35、1:40、1:42、1:45 or 1:50 etc., preferably 1:
(0.5-30)。
Preferably, the reducing agent is any one in magnesium, zinc, aluminium, lithium, sodium or potassium or at least two
Mixture, mixture typical case but non-limiting examples have：The mixture of magnesium and zinc, zinc and aluminium it is mixed
Mixture of the mixture of compound, magnesium and lithium, aluminium and sodium etc..
Preferably, the inert atmosphere is in nitrogen atmosphere, argon gas atmosphere, helium atmosphere or hydrogen atmosphere
Any one or at least two combination；
Preferably, the acid is hydrochloric acid and/or sulfuric acid.
" hydrochloric acid and/or sulfuric acid " of the present invention refers to：It can be hydrochloric acid or sulfuric acid, can also be
The mixture of hydrochloric acid and sulfuric acid.
Preferably, the concentration of the hydrochloric acid be the mol/L of 0.01 mol/L -12, preferably 3 mol/Ls,
Preferably, the concentration of the sulfuric acid is the mol/L of 0.01 mol/L -16, preferably 4 mol/Ls.
In the present invention, two in micro-nano structure carbon/SiO 2 composite microsphere are reduced by metallothermic processes
Silica core, and then micron structured carbon silicon complex microsphere is obtained, because the volume of reduzate silicon is less than two
The volume of silica precursors, has directly obtained the micro-nano knot with core-hollow shell structure in the case of without template
Structure carbon silicon complex microsphere, the micro-nano structure carbon silicon complex microsphere includes core, hollow shell and in core and sky
Cavity between heart shell, the core is silicon ball, and the hollow shell is carbon hollow shell.
As preferred embodiment, this method comprises the following steps：
(1) using water or organic solvent as solvent, nano SiO 2 particle, protective agent and carbon nanometer material are prepared
The mixed solution of material, as the precursor solution of spray drying, using atomizer by the presoma of spray drying
Solution atomization is spray-dried into drop.During spray drying, charging rate is
0.5mL/min-100mL/min, EAT is 120 DEG C -220 DEG C, and leaving air temp automatically adjusts for equipment,
Carrier gas is air or inert gas.
Second aspect, the present invention provides the micro-nano structure carbon that a kind of method as described in relation to the first aspect is prepared
Silicon complex microsphere, the micro-nano structure complex microsphere be core-hollow shell structure carbon silicon grain, including core,
Hollow shell and the cavity between core and hollow shell, the core are silicon ball, a diameter of 3nm-200nm；It is described
Hollow shell is carbon hollow shell, and thickness is 1nm-50nm.
A diameter of 3nm-200nm of silicon ball of the present invention, for example can for 3nm, 5nm, 10nm,
15nm、25nm、30nm、40nm、50nm、60nm、65nm、70nm、80nm、90nm、
100nm, 120nm, 130nm, 150nm, 160nm, 170nm, 180nm, 185nm, 190nm or
200nm etc..
The thickness of carbon hollow shell of the present invention be 1nm-50nm, for example can for 1nm, 3nm, 5nm,
8nm、10nm、13nm、15nm、20nm、25nm、28nm、30nm、35nm、40nm、
45nm or 50nm etc..
In micro-nano structure complex microsphere of the present invention, silicon core is transformed by silica, and carbon is empty
Heart shell is transformed by protective agent.
In the present invention, described micro-nano structure carbon silicon complex microsphere be shaped as spherical, parachute-shaped, it is ellipse
One or more kinds of combinations in spherical or irregular shape.
Preferably, the particle diameter of the micro-nano structure carbon silicon complex microsphere is 0.5 μm -50 μm, for example, can be
0.5μm、1μm、2μm、5μm、8μm、10μm、12μm、15μm、18μm、20μm、
21μm、25μm、28μm、30μm、32μm、35μm、38μm、40μm、42μm、45μm、
48 μm or 50 μm.
Preferably, the weight percentage of silicon ball is in the micro-nano structure carbon silicon complex microsphere
50%-99%, for example can for 50%, 55%, 60%, 62%, 65%, 70%, 75%, 78%,
80%th, 85%, 90% or 99% etc..
It is used as the optimal technical scheme of micro-nano structure carbon silicon complex microsphere of the present invention, the micro-nano structure
Change and carbon nanomaterial is also included in carbon silicon complex microsphere, the carbon silicon of the carbon nanomaterial and core-hollow shell structure
Particle mixing constitutes micro-nano structure carbon silicon complex microsphere.
The third aspect, the present invention provides the use of the micro-nano structure carbon silicon complex microsphere as described in second aspect
On the way, the micro-nano structure carbon silicon complex microsphere is used as lithium ion battery active cathode material.
Micro-nano structure carbon silicon complex microsphere of the present invention is used for lithium ion secondary as active cathode material
It in battery, can be used alone, can also be used in mixed way with other active cathode materials, it is negative with other activity
When pole material is used in mixed way as ion secondary battery cathode material lithium, the micro-nano structure carbon silicon used is combined
The consumption of microballoon is not less than the 1% of total negative active core-shell material.
Other described active cathode materials include Delanium, native graphite, single-walled carbon nanotube, few layer carbon
Nanotube, multi-walled carbon nanotube, graphene, the graphene oxide of reduction, hard carbon material, can occur with lithium
The mistake of conversion reaction can occur for the metal and its precursor (tin, germanium, aluminium, cobalt etc.) of alloying reaction and lithium
Cross metallic compound (cobalt oxide, iron oxide etc.) and embedding lithium type transition metal oxide (lithium titanate etc.).
Fourth aspect, the present invention provides a kind of electrochemical energy storing device and/or energy-storage system, it is characterised in that
The electrochemical energy storing device and/or energy-storage system are combined micro- comprising the micro-nano structure carbon silicon described in second aspect
Ball.
Compared with prior art, the present invention at least has the advantages that：
(1) present invention passes through spray drying, heat treatment by being used as raw material from silica and protective agent
And the reasonable process cooperation of metallothermic processes prepares the micro-nano knot with core-hollow shell structure there is provided a kind of
The method of structure carbon silicon complex microsphere, method of the invention constructs core-template needed for hollow shell structure without any
Introducing and removal, by being simply spray-dried, being heat-treated and metallothermic processes can be achieved, have
Process route is simple, it is low to consume energy, can scale and the advantages of the cost of raw material low in cost and easily available.
(2) the micro-nano structure carbon silicon complex microsphere prepared by the present invention has core-hollow shell structure, including two
The silicon ball that silica is transformed as core, the carbon hollow shell that protective agent is transformed as hollow shell, and
Cavity between core and hollow shell, micro-nano structure carbon silicon complex microsphere of the invention is used as lithium-ion electric
During the negative material of pond, the characteristic (nano-scale of the silicon nanometer core due to being integrated with carbon hollow shell parcel：Silicon is received
Rice core is conducive to the release of stress caused by electronics and the transmission of lithium ion and silicon Volume Changes；Core-hollow shell
Structure：Enough spaces are provided for the volumetric expansion of silicon materials, bonding between silicon core and carbon shell is prevented
It is broken, the destruction this not only avoids silicon volumetric expansion to outside electrode structure, so as to ensure that material structure
Integrality and stability, also restrained effectively silicon nano material surface SEI continuous formation, stabilize
The surface and interface of material, is conducive to the raising of coulombic efficiency and cyclical stability) and its micron structured (have
Beneficial to the raising of material tap density, so that its volume and capacity ratio and energy density are improved, so that convenient battery
Miniaturization) advantage, show extremely excellent discharge and recharge volume and capacity ratio and cyclical stability, wherein
Under 0.5C current density, it has up to 1590mAh/cm3Volume and capacity ratio；In 1C electric current
After being circulated 50 times under density, capability retention is up to 94%.
Brief description of the drawings
Fig. 1 schemes for the TEM of aerosil；
Fig. 2 schemes for the SEM of the gained micro-nano structure carbon silicon complex microsphere of embodiment 1；
Fig. 3 schemes for the low power TEM of the gained micro-nano structure carbon silicon complex microsphere of embodiment 1；
The high power TEM figures of Fig. 4 gained micro-nano structure carbon silicon complex microspheres of embodiment 1.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1
20nm silica (as shown in Figure 1) and D/W are mixed, spraying is used as
Dry precursor solution；In the precursor solution, solute concentration is 15wt%；During spray drying, charging
Speed is 10mL/min, and EAT is 150 DEG C, and leaving air temp is 80 DEG C, and carrier gas is air；Obtain
Powder is heat-treated 2h under 500 DEG C of hydrogen, and micro-nano structure carbon-SiO 2 composite microsphere is made；Made with magnesium
For reducing agent (gained powder quality ratio and reducing agent mass ratio 1：1), by obtained micro-nano structure carbon-dioxy
SiClx complex microsphere is in the mixed atmosphere of hydrogen and argon gas after 650 DEG C of reductase 12 h, 3 mol/L HCl processing
Micro-nano structure carbon silicon complex microsphere is obtained afterwards, and the granularity of obtained micro-nano structure carbon silicon complex microsphere exists
1-5 μm, as a result as shown in Fig. 2,3 and 4, carbon-silicon compound is in micron level spherical (Fig. 2), by nanoscale
Particle constitutes (Fig. 3), and these nano-scale particles have silicon core-carbon hollow ball structure (Fig. 4)；Wherein, silicon
Weight percentage be 99%.
By obtained micro-nano structure carbon silicon complex microsphere, binding agent polyvinylidene fluoride (PVDF), conduction
Agent acetylene black is uniformly hybridly prepared into slurry in 1-METHYLPYRROLIDONE (NMP), is then applied to copper
On paper tinsel collector, it is dried in vacuo 12 hours back rollers at 120 DEG C and is pressed into cathode pole piece；Using cathode pole piece as survey
Electrode is tried, using metallic lithium foil as to electrode, electrolyte is 1M LiPF6/EC:DEC(1:1；V/v), it is instant
Solution has the ethylene carbonate of lithium hexafluoro phosphate and the mixed solvent of diethyl carbonate, and barrier film is Celgard 2400,
Button-shaped lithium ion battery is assembled into the glove box that oxygen and water content are respectively less than 1ppm.In 0.5C electricity
Under current density, it has up to 1590mAh/cm3Volume and capacity ratio；Circulated under 1C current density
After 50 times, capability retention is up to 94%.
Embodiment 2
The dichloroethane solution of 5nm silica and polystyrene is mixed, spray drying is used as
Precursor solution；In the precursor solution, solute concentration is 0.1wt%.During spray drying, charging rate is
0.5mL/min, EAT is 100 DEG C, and leaving air temp is 70 DEG C, and carrier gas is air.The powder of acquisition exists
30min is heat-treated under 900 DEG C of argon gas, micro-nano structure carbon-SiO 2 composite microsphere is made；Using magnesium as also
Former agent (gained powder quality ratio and reducing agent mass ratio 1：0.6), by obtained micro-nano structure carbon-silica
Complex microsphere is in the mixed atmosphere of hydrogen and argon gas after 800 DEG C of reduction 0.5h, and 4 mol/L sulfuric acid treatments are obtained
The carbon silicon complex microsphere obtained, is made micro-nano structure carbon silicon complex microsphere；Obtained micro-nano structure carbon silicon
The granularity of complex microsphere is at 0.5-2 μm；Wherein, the weight percentage of silicon is 84%.
Follow-up test such as embodiment 1.Under 0.5C current density, it has up to 1452mAh/cm3's
Volume and capacity ratio；After being circulated 50 times under 1C current density, capability retention is up to 90%.
Embodiment 3
The aqueous solution of 100nm silica dioxide granule, CNT and starch is mixed, spraying is used as
Dry precursor solution；In the precursor solution, solute concentration is 60wt%.During spray drying, charging
Speed is 95mL/min, and EAT is 220 DEG C, and leaving air temp is 100 DEG C, and carrier gas is argon gas.Obtain
Powder be heat-treated 6h under 700 DEG C of nitrogen, micro-nano structure carbon-SiO 2 composite microsphere is made；With potassium
It is used as reducing agent (gained powder quality ratio and reducing agent mass ratio 1：3), by obtained micro-nano structure carbon-two
Silica complex microsphere is reduced after 48h for 100 DEG C in the mixed atmosphere of hydrogen and argon gas, 3 mol/L HCl
The complex microsphere obtained is handled, micro-nano structure carbon silicon complex microsphere is made；Obtained micro-nano structure carbon
The granularity of silicon complex microsphere is at 15-50 μm；Wherein, the weight percentage of silicon is 50%.
Follow-up test such as embodiment 1.Under 0.5C current density, it has up to 1212mAh/cm3's
Volume and capacity ratio；After being circulated 45 times under 1C current density, capability retention is up to 96%.
Embodiment 4
300nm silica dioxide granule, graphene oxide and the fructose aqueous solution are mixed, spray is used as
The precursor solution that mist is dried；In the precursor solution, solute concentration is 40wt%.During spray drying, enter
Material speed is 55mL/min, and EAT is 300 DEG C, and leaving air temp is 150 DEG C, and carrier gas is air.Obtain
The powder obtained is heat-treated 12h under 420 DEG C of helium, and micro-nano structure carbon-SiO 2 composite microsphere is made；With
Zinc powder is used as reducing agent (gained powder quality ratio and reducing agent mass ratio 1：30), by obtained micro-nano structure
Carbon-SiO 2 composite microsphere is reduced after 12h for 1000 DEG C in the mixed atmosphere of hydrogen and argon gas, 3 moles/
The complex microsphere that HCl processing is obtained is risen, micro-nano structure carbon silicon complex microsphere is made；Obtained micro-nano knot
The granularity of structure carbon silicon complex microsphere is at 5-15 μm；Wherein, the weight percentage of silicon is 75%.
Follow-up test such as embodiment 1.Under 0.5C current density, it has up to 1350mAh/cm3's
Volume and capacity ratio；After being circulated 60 times under 1C current density, capability retention is up to 95%.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention by above-described embodiment
Above-mentioned method detailed is not limited to, that is, does not mean that the present invention has to rely on above-mentioned method detailed ability real
Apply.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and the addition of auxiliary element, the selection of concrete mode etc., all fall within the guarantor of the present invention
Within the scope of protecting scope and being open.
Claims (10)
1. a kind of preparation method of micro-nano structure carbon silicon complex microsphere, it is characterised in that methods described bag
Include following steps：
Using silica dioxide granule and protectant mixed solution as the precursor solution of spray drying, sprayed
Mist is dried and is heat-treated, and is prepared micro-nano structure carbon/SiO 2 composite microsphere, then, is passed through gold
Category thermal reduction prepares micro-nano structure carbon silicon complex microsphere.
2. the method as described in claim 1, it is characterised in that the protective agent is glucose, sugarcane
It is sugar, fructose, maltose, chitosan, citric acid, urea, ascorbic acid, starch, protein, bright
It is glue, Arabic gum, alginate, cellulose, phenolic resin, polyvinylidene fluoride, polyaminoacid, poly-
Vinylpyrrolidone, poly- carbon ester, polyvinyl alcohol, polyethylene glycol, polymethyl methacrylate, poly- methyl-prop
It is any in olefin(e) acid ethyl ester, polyacrylic resin, polyvinyl chloride, polyacrylonitrile, PLA or polystyrene
It is a kind of or at least two mixture.
3. method as claimed in claim 1 or 2, it is characterised in that the silica dioxide granule is gas phase
Silica dioxide granule；
Preferably, the particle diameter of the silica dioxide granule is 5nm-300nm；
Preferably, in the precursor solution of the spray drying, solvent is water and/or organic solvent；
Preferably, in the precursor solution of the spray drying, the mass concentration of solute is 0.1%-60%,
Preferably 15%；
Preferably, the silica and protectant mass ratio are 1:(0.1-50)；
Preferably, carbon nanomaterial is also included in the precursor solution of the spray drying；
Preferably, the carbon nanomaterial is CNT, graphene, graphene oxide, the stone of reduction
In black olefinic oxide, carbon fiber any one or at least two mixture.
4. the method as described in claim any one of 1-3, it is characterised in that the charging of the spray drying
Speed is 0.5mL/min-100mL/min, preferably 10mL/min-60mL/min；
Preferably, the EAT of the spray drying is 100 DEG C -300 DEG C, preferably 120 DEG C -220 DEG C；
Preferably, the leaving air temp of the spray drying is automatically adjusted by equipment；
Preferably, the carrier gas of the spray drying is air or inert gas；
Preferably, in the spray drying, the precursor solution of spray drying is atomized into using atomizer
Drop, the atomizer is power formula atomizer, pneumatic atomizer, rotary atomizer or ultrasonic ultrasonic delay line memory
In any one.
5. the method as described in claim any one of 1-4, it is characterised in that the heat treatment is non-oxide
Carried out under atmospheric condition；
Preferably, the nonoxidizing atmosphere is in helium atmosphere, neon atmosphere, argon gas atmosphere or hydrogen atmosphere
Any one or at least two combination, more preferably argon gas atmosphere and/or hydrogen atmosphere；
Preferably, the temperature of the heat treatment is 300 DEG C -1000 DEG C, more preferably 400 DEG C
-900℃；
Preferably, the heat treatment time is 30min-24h, more preferably 2h-12h.
6. the method as described in claim any one of 1-5, it is characterised in that the metallothermic reduction legal system
It is for micro-nano structure carbon silicon complex microsphere process：By micro-nano structure carbon/SiO 2 composite microsphere with going back
Former agent mixing, is warming up to 100 DEG C -1200 DEG C, reduces 0.5h-60h, be cooled to room temperature under an inert atmosphere,
With drying is washed after acid soak, micro-nano structure carbon silicon complex microsphere is obtained；
Preferably, the mass ratio of the micro-nano structure carbon/SiO 2 composite microsphere and reducing agent is 1:
(0.1-50), more preferably 1:(0.5-30)；
Preferably, the reducing agent is any one in magnesium, zinc, aluminium, lithium, sodium or potassium or at least two
Mixture；
Preferably, the inert atmosphere is in nitrogen atmosphere, argon gas atmosphere, helium atmosphere or hydrogen atmosphere
Any one or at least two combination；
Preferably, the acid is hydrochloric acid and/or sulfuric acid, and the concentration of the hydrochloric acid is preferably 3 mol/Ls, institute
The concentration for stating sulfuric acid is 4 mol/Ls.
7. the micro-nano structure carbon silicon that a kind of such as any one of claim 1-6 methods describeds are prepared is combined micro-
Ball, it is characterised in that the micro-nano structure carbon silicon complex microsphere is the carbon silicon of core-hollow shell structure
Grain, including core, hollow shell and the cavity between core and hollow shell, the core are silicon ball, a diameter of
3nm-200nm；The hollow shell is carbon hollow shell, and thickness is 1nm-50nm；
Preferably, the particle diameter of the micro-nano structure carbon silicon complex microsphere is 0.5 μm -50 μm；
Preferably, the weight percentage of silicon ball is in the micro-nano structure carbon silicon complex microsphere
50%-99%.
8. micro-nano structure carbon silicon complex microsphere according to claim 7, it is characterised in that described
Carbon nanomaterial, the carbon nanomaterial and core-hollow shell are also included in micro-nano structure carbon silicon complex microsphere
The carbon silicon grain mixing of structure constitutes micro-nano structure carbon silicon complex microsphere.
9. a kind of micro-nano structure carbon silicon complex microsphere as claimed in claim 7 or 8 is used as lithium ion battery
The purposes of active cathode material.
10. a kind of electrochemical energy storing device and/or energy-storage system, it is characterised in that the electrochemical energy storage
Device and/or energy-storage system include the micro-nano structure carbon silicon complex microsphere described in claim 7 or 8.
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