CN105609711A - Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof - Google Patents
Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a micro-nano structured silicon-carbon composite microsphere, a preparation method and an application thereof. According to the method, a porous silicon nano-material conversed during an industrial smelting process of alloys such as metal silicon and iron silicon is composited to carbon and/or a carbon nano material conversed by a protective agent in a one-step manner through a spray drying method, and the micro-nano structured silicon-carbon composite microsphere can be prepared. The preparation method has the advantages of low cost, simple process, low energy consumption, and large-scale preparation, and the obtained micro-nano structured silicon-carbon composite microsphere as a lithium ion battery cathode material has high-volume and capacity ratio and stable circulation during a charge and discharge process.
Description
Technical field
The present invention relates to lithium ion battery negative material technical field, be specifically related to a kind of complex microsphere and system thereofPreparation Method and application, relate in particular to a kind of micro-nano structure SiClx carbon complex microsphere and its preparation method and application.
Background technology
Silicon can be used as a kind of graphite that replaces at secondary cell, the especially negative active core-shell material in lithium ion battery,It has better capacity. But silicon materials with huge Volume Changes, produce in charge and discharge processMechanical stress cause the disengaging between efflorescence and structural breakdown and material and the collector of active material, thereby makeOne-tenth capacity is decay and cycle performance of battery reduction rapidly. In addition,, due to this Volumetric expansion, silicon is at electricitySeparate in liquid and be difficult to form stable solid electrolyte interface SEI film, cause efficiency for charge-discharge to reduce, accelerate to followThe further deterioration of ring performance. By nano-structured silicon materials and/or porous and then tie with carbon nanomaterialClose construct nano composite material can solve to a certain extent silicon in charge and discharge process due to volumetric expansion effectThe structure that should cause and surface and interface instability problem, thereby improve, it discharges and recharges, cycle performance.
Silicon ash is also cohesion silicon ash or SILICA FUME, is at materials such as smelting commercial silicon (metallic silicon), ferro-siliciumsThe very strong silica (SiO of a large amount of volatility producing in ore-smelting electric furnace when material2) and silicon (Si) gas rowAfter putting, in air, oxidation rapidly, condensation, precipitation form. It is the accessory substance during large industry is smelted,Its main chemical compositions is SiO2, can reach more than 98%. Silicon ash outward appearance is grey or canescence, by surfaceFor smooth spherical SiO2Particle composition, its particle size is less than 1000nm, and average-size is at 100nm extremelyBetween 300nm, there are 50～70 times to the specific area of flyash.
At present, the international total output of silicon ash is more than 800,000 tons/year, along with the whole world is to ferro-silicium, silicon goldThe expansion of the demand of genus material and the reinforcement to environmental protection dynamics, silicon ash resource can be more and more abundanter. Recently, IDirectly adopt metallothermic processes to reduce the silicon producing in the alloy processes such as industrial metal smelting silicon, iron siliconAsh makes silicon nano material; It is mixed with material with carbon element ball milling and/or carbon precursor, through hydrothermal carbonization, solventHeat treatment, pyrolysis carbonization, or the method for chemical vapor carbon deposition makes the silicon/carbon composite of nano-scale,For the preparation of the high performance silicon for lithium ion battery negative and other energy-storage system and Si-C composite material providesA kind of raw material resources abundant, cheap and easy to get, technique is simple, with low cost and be easy to amplify method.
Nano-structured and/or porous that it should be noted that material has directly caused active electricity conventionallyThe tap density of utmost point material reduces greatly, has seriously restricted the lifting of its volume and capacity ratio and energy density per unit volume,Hinder the microminiaturization of battery and/or relevant energy-storage system. Research shows, constructs silicon or the silicon with micro-/micro-nano structureCarbon composite is a kind of effective way (HighVolumetricCapacity addressing the above problemSilicon-BasedLithiumBatteryAnodesbyNanoscaleSystemEngineering,NanoLetters2013,13,5578；Apomegranate-inspirednanoscaledesignforlarge-volume-changelithiumbatteryanodes,NatureNanotechnology2014,9,187)。
But current micro-nano structure SiClx or Si-C composite material mainly rely on the gas such as the monosilane of high riskState silicon source, or business silica flour or silicon grain or the silicon quantum dot of expensive solid construction or be unfavorable for environmentHf etching process or harshness (such as, high vacuum, high temperature etc.) power consumption building-up process, material andPerformance performance and the practical application of such micro-nano structure composite of the serious restriction of method itself. Therefore findA kind of technique is simple, energy consumption is low and can scale, and method with low cost is carried out the preparation of silicon-carbon complex microsphereIt is current problem demanding prompt solution.
Summary of the invention
The object of the present invention is to provide a kind of complex microsphere and its preparation method and application, particularly a kind of micro-Micro-nano structure SiClx carbon complex microsphere and its preparation method and application.
For reaching this goal of the invention, the present invention by the following technical solutions:
First aspect, the invention provides a kind of micro-nano structure SiClx carbon complex microsphere, described micro-nano structureThe carbon that SiClx carbon complex microsphere is transformed by silicon nano material and protective agent forms; Or by silicon nano material andThe carbon that protective agent transforms and carbon nanomaterial composition.
In the present invention, the particle diameter of described micro-nano structure carbon silicon complex microsphere is 0.5-50 μ m, for example, can be0.5μm、1μm、2μm、5μm、8μm、10μm、12μm、15μm、18μm、20μm、21μm、25μm、28μm、30μm、32μm、35μm、38μm、40μm、42μm、45μm、48μm、50μm，Preferably, in described micro-nano structure carbon silicon complex microsphere, the weight percentage of silicon is 50-99%.
In the present invention, described micro-nano structure SiClx carbon complex microsphere be shaped as spherical, parachute-shaped, ellipseThe combination of one or more in spherical or irregularly shaped.
In the present invention, described silicon nano material is by institute in the alloy process of industrial metal smelting silicon or iron siliconThe silicon ash producing is transformed; Preferably, described silicon nano material has loose structure.
In the present invention, described protective agent is glucose, sucrose, fructose, maltose, shitosan, lemonAcid, urea, ascorbic acid, starch, protein, gelatin, Arabic gum, alginate, cellulose,Phenolic resins, polyvinylidene fluoride, polyaminoacid, polyvinylpyrrolidone, poly-carbon ester, polyvinyl alcohol,Polyethylene glycol, polymethyl methacrylate, polyethyl methacrylate, polyacrylic resin, polyvinyl chloride,The mixture of any one in polyacrylonitrile, PLA or polystyrene or at least two kinds.
In the present invention, described carbon nanomaterial is CNT, Graphene, graphene oxide, reductionGraphene oxide, carbon fiber, bacteria cellulose based carbon fiber or bacteria cellulose class carbon cilium in appointThe mixtures a kind of or at least two kinds of anticipating.
Second aspect, the present invention also provides the micro-nano structure SiClx carbon as described in first aspect present invention compoundThe preparation method of microballoon, the method is taking water or organic solvent as solvent, by silicon nano material and protectant mixedClose solution or the mixed solution of silicon nano material, protective agent and carbon nanomaterial is obtained by spray drying processMicro-nano structure SiClx carbon complex microsphere.
In the present invention, described obtains micro-nano structure SiClx carbon complex microsphere by spray drying process, refers to useBe heated and make its solvent evaporates in hothouse internal cause in spray-dired mixed solution, directly obtaining silicon-carbon compoundMicroballoon;
Or described mixed solution obtains after microballoon by spray drying process, further by non-oxide gasUnder atmosphere heat treatment make protective agent in microballoon and/or carbon nanomaterial generation carbonization and or sex change, obtain silicon-carbon multipleClose microballoon.
In the present invention, described non-oxidizing atmosphere is in nitrogen, argon gas, hydrogen, helium or carbon dioxideThe mixture of any one or at least two kinds.
As preferred detailed description of the invention, the method comprises the following steps:
Taking water or organic solvent as solvent, silicon nano material and the protective agent aqueous solution are mixed, as sprayThe precursor solution that mist is dry; Described precursor solution is atomized into drop, when spraying is dry, charging speedDegree is for 0.5-100mL/min, and EAT is 100-300 DEG C, and leaving air temp is 100 DEG C, carrier gas be air orInert gas; The powder obtaining continues dry under 500 DEG C of hydrogen, makes micro-nano structure SiClx carbon complex microsphere.
In the present invention, described precursor solution is by pressure atomizer, pneumatic atomizer, rotaryAny one in atomizer or ultrasonic ultrasonic delay line memory is atomized into drop.
In the present invention, in described precursor solution, solute concentration is 0.1-60wt%, is preferably 15%.
The third aspect, the present invention also provides micro-structural silicon-carbon complex microsphere as described in first aspect present inventionAs the purposes of lithium ion battery active cathode material.
Micro-nano structure SiClx carbon complex microsphere of the present invention is used for lithium ion secondary as active cathode materialIn battery; Mix with other active cathode material while being used as ion secondary battery cathode material lithium, useThe consumption of micro-nano structure SiClx carbon complex microsphere be not less than 1% of total negative active core-shell material.
Described other active cathode material comprise Delanium, native graphite, SWCN, few layer carbonThe graphene oxide of nanotube, multi-walled carbon nano-tubes, Graphene, reduction, hard carbon material, can occur with lithiumThe metal of alloying reaction and precursor thereof (tin, germanium, aluminium, cobalt etc.), can there is the transition of conversion reaction with lithiumMetallic compound (cobalt oxide, iron oxide etc.) and embedding lithium type transition metal oxide (lithium titanate etc.).
Fourth aspect, the present invention also provides a kind of electrochemical energy storing device and/or energy-storage system, described electrificationLearning energy storage device and/or energy-storage system, to comprise micro-nano structure SiClx carbon as described in first aspect present invention compound micro-Ball.
Compared with prior art, the present invention at least has following beneficial effect:
(1) the present invention is mainly from the silicon ash by producing the alloy processes such as industrial metal smelting silicon, iron siliconThe porous silicon nano material being transformed is set out, provide one prepare micro-nano structure SiClx carbon complex microsphere lithium fromSub-cell negative electrode material and preparation method thereof, the method have the cost of raw material cheap, be easy to get, preparation technologySimply, consume energy low, the advantage such as can amplify.
(2) the prepared micro-nano structure SiClx carbon complex microsphere of the present invention is as lithium ion battery negative materialTime, due to the integrated characteristic (nano-scale: be conducive to electronics and lithium ion of porous silicon nano material selfTransmission, and the release of the stress that causes of silicon Volume Changes; Loose structure: effectively hold the swollen of silicon volumeSwollen, thus ensured nano material self structure integrality, avoided silicon volumetric expansion to outer electrode structureThe destruction of making) with and micrometer structure (be conducive to the raising of material tap density, thereby improve its volumeSpecific capacity and energy density per unit volume, thereby the microminiaturization of convenient battery) advantage, show extremely excellent fillingSpecific discharge capacity and cyclical stability, wherein, under the current density of 0.5C, it has up to 1586mAh/cm3Volume and capacity ratio; Under the current density of 1C, circulate after 50 times, capability retention can reach 95%.
Brief description of the drawings
Fig. 1 silicon that the silicon ash that produces in the alloy processes such as industrial metal smelting silicon, iron silicon is transformed of serving as reasonsThe TEM figure of nano material;
Fig. 2 is the SEM figure of embodiment 1 gained micro-nano structure SiClx carbon complex microsphere;
Fig. 3 is the TEM figure of embodiment 1 gained micro-nano structure SiClx carbon complex microsphere.
Detailed description of the invention
Further illustrate technical scheme of the present invention below by detailed description of the invention. Those skilled in the artShould understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment 1
By being transformed by the silicon ash producing in the alloy processes such as industrial metal smelting silicon, iron silicon of appropriate concentration andThe silicon nano material (as shown in Figure 1) and the D/W that come mix, before spray-diredDrive liquid solution; In this precursor solution, solute concentration is 15wt%; When spraying is dry, charging rate is10mL/min, EAT is 150 DEG C, and leaving air temp is 80 DEG C, and carrier gas is air; The powder obtaining existsUnder 500 DEG C of hydrogen, continue to be dried, make micro-nano structure SiClx carbon complex microsphere; Prepared micro-nano structure SiClxThe granularity of carbon complex microsphere is at 1-5 μ m, and result as shown in Figures 2 and 3; Wherein, the weight percentage of silicon is99％。
By the micro-nano structure SiClx carbon complex microsphere making, binding agent polyvinylidene fluoride (PVDF), conductionAgent acetylene black is even mixed preparing form slurry in 1-METHYLPYRROLIDONE (NMP), is then applied to copperOn paper tinsel collector body, 120 DEG C of vacuum drying after 12 hours roll-in make cathode pole piece; Taking cathode pole piece as surveyExamination electrode, taking metallic lithium foil as to electrode, electrolyte is 1MLiPF6/EC:DEC (1:1; V/v), instantSolution has the ethylene carbonate of lithium hexafluoro phosphate and the mixed solvent of diethyl carbonate, and barrier film is Celgard2400,In being all less than the glove box of 1ppm, oxygen and water content be assembled into button-shaped lithium ion battery. At the electricity of 0.5CUnder current density, it has up to 1586mAh/cm3Volume and capacity ratio; Under the current density of 1C, circulateAfter 50 times, capability retention can reach 95%.
Embodiment 2
By being transformed by the silicon ash producing in the alloy processes such as industrial metal smelting silicon, iron silicon of appropriate concentration andThe silicon nano material coming and the dichloroethane solution of polystyrene mix, as spray-dired presomaSolution; In this precursor solution, solute concentration is 0.1wt%. When spraying is dry, 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 obtaining is under 900 DEG C of argon gasContinue to be dried, make micro-nano structure SiClx carbon complex microsphere; Prepared micro-nano structure SiClx carbon complex microsphereGranularity at 0.5-2 μ m; Wherein, the weight percentage of silicon is 84%.
Follow-up test is as embodiment 1. Under the current density of 0.5C, it has up to 1453mAh/cm3'sVolume and capacity ratio; Under the current density of 1C, circulate after 50 times, capability retention can reach 92%.
Embodiment 3
By being transformed by the silicon ash producing in the alloy processes such as industrial metal smelting silicon, iron silicon of appropriate concentration andThe aqueous solution of silicon nano material, CNT and the starch coming mixes, as spray-dired presomaSolution; In this precursor solution, solute concentration is 60wt%. When spraying is dry, charging rate is 95mL/min,EAT is 220 DEG C, and leaving air temp is 100 DEG C, and carrier gas is argon gas. The powder obtaining is at 700 DEG C of nitrogenLower continuation is dry, makes micro-nano structure SiClx carbon complex microsphere; Prepared micro-nano structure SiClx carbon is compound micro-The granularity of ball is at 15-50 μ m; Wherein, the weight percentage of silicon is 50%.
Follow-up test is as embodiment 1. Under the current density of 0.5C, it has up to 1222mAh/cm3'sVolume and capacity ratio; Under the current density of 1C, circulate after 45 times, capability retention can reach 98%.
Embodiment 4
By being transformed by the silicon ash producing in the alloy processes such as industrial metal smelting silicon, iron silicon of appropriate concentration andThe silicon nano material, graphene oxide and the fructose water solution that come mix, as spray-dired forerunnerLiquid solution; In this precursor solution, solute concentration is 40wt%. When spraying is dry, charging rate is55mL/min, EAT is 300 DEG C, and leaving air temp is 150 DEG C, and carrier gas is air. The powder obtaining existsUnder 420 DEG C of helium, continue to be dried, make micro-nano structure SiClx carbon complex microsphere; Prepared micro-nano structure SiClxThe granularity of carbon complex microsphere is at 5-15 μ m; Wherein, the weight percentage of silicon is 75%.
Follow-up test is as embodiment 1. Under the current density of 0.5C, it has up to 1352mAh/cm3'sVolume and capacity ratio; Under the current density of 1C, circulate after 60 times, capability retention can reach 94%.
Applicant's statement, the present invention illustrates process of the present invention by above-described embodiment, but the present inventionBe not limited to above-mentioned processing step, do not mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention is selected former to the present inventionThe selections of the equivalence replacement of material and the interpolation of auxiliary element, concrete mode etc., all drop on protection model of the present inventionWithin enclosing and disclosing scope.
Claims (10)
1. a micro-nano structure SiClx carbon complex microsphere, is characterized in that, described micro-nano structure SiClx carbon is multipleClosing microballoon is made up of the carbon of silicon nano material and protective agent conversion; Or turned by silicon nano material and protective agentThe carbon of changing and carbon nanomaterial composition.
2. micro-nano structure carbon silicon complex microsphere as claimed in claim 1, is characterized in that described micro-nanoThe particle diameter of structuring carbon silicon complex microsphere is 0.5-50 μ m;
Preferably, in described micro-nano structure carbon silicon complex microsphere, the weight percentage of silicon is 50-99%.
3. micro-nano structure carbon silicon complex microsphere as claimed in claim 1 or 2, is characterized in that, described inSilicon nano material be the silicon ash that produces in the alloy process by industrial metal smelting silicon or iron silicon transform andCome; Preferably, described silicon nano material has loose structure;
Preferably, described protective agent be glucose, sucrose, fructose, maltose, shitosan, citric acid,Urea, ascorbic acid, starch, protein, gelatin, Arabic gum, alginate, cellulose, phenolic aldehydeResin, polyvinylidene fluoride, polyaminoacid, polyvinylpyrrolidone, poly-carbon ester, polyvinyl alcohol, poly-secondGlycol, polymethyl methacrylate, polyethyl methacrylate, polyacrylic resin, polyvinyl chloride, poly-The mixture of any one in acrylonitrile, PLA or polystyrene or at least two kinds;
Preferably, described carbon nanomaterial is CNT, Graphene, graphene oxide, reductionIn graphene oxide, carbon fiber, bacteria cellulose based carbon fiber or bacteria cellulose class carbon cilium arbitrarilyA kind of or the mixture of at least two kinds.
4. the preparation method of the micro-nano structure SiClx carbon complex microsphere as described in claim 1-3 any one, itsBe characterised in that, taking water or organic solvent as solvent, by silicon nano material and protectant mixed solution or by siliconThe mixed solution of nano material, protective agent and carbon nanomaterial obtains micro-nano structure SiClx by spray drying processCarbon complex microsphere.
5. preparation method according to claim 4, is characterized in that, the described spray drying process of passing throughObtain micro-nano structure SiClx carbon complex microsphere, refer to for spray-dired mixed solution and be subject in hothouse internal causeHeat and make its solvent evaporates, directly obtain silicon-carbon complex microsphere;
Or described mixed solution obtains after microballoon by spray drying process, further by non-oxide gasUnder atmosphere heat treatment make protective agent in microballoon and/or carbon nanomaterial generation carbonization and or sex change, obtain silicon-carbon multipleClose microballoon.
6. preparation method according to claim 5, is characterized in that, described non-oxidizing atmosphere isThe mixture of any one in nitrogen, argon gas, hydrogen, helium or carbon dioxide or at least two kinds.
7. according to the preparation method described in claim 4-6 any one, it is characterized in that, the method comprise withLower step:
Taking water or organic solvent as solvent, silicon nano material and the protective agent aqueous solution are mixed, as sprayThe precursor solution that mist is dry; Described precursor solution is atomized into drop, when spraying is dry, charging speedDegree is 0.5-100mL/min, and EAT is 100-300 DEG C, and leaving air temp is 100 DEG C, and carrier gas is airOr inert gas; The powder obtaining continues dry under 500 DEG C of hydrogen, makes micro-nano structure SiClx carbon compoundMicroballoon.
8. preparation method as claimed in claim 7, is characterized in that, described precursor solution is by pressingAny one atomization in power formula atomizer, pneumatic atomizer, rotary atomizer or ultrasonic ultrasonic delay line memoryBecome drop;
Preferably, in described precursor solution, solute concentration is 0.1-60wt%, is preferably 15%.
9. the micro-nano structure SiClx carbon complex microsphere as described in claim 1-3 any one is as lithium ion batteryThe purposes of active cathode material.
10. electrochemical energy storing device and/or an energy-storage system, is characterized in that, described electrochemical energy storage devicePart and/or energy-storage system comprise the micro-nano structure SiClx carbon complex microsphere as described in claim 1-3 any one.
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| CN106784661A (en) * | 2016-12-02 | 2017-05-31 | 黑龙江科技大学 | A kind of preparation method of the graphene/silicon porous microsphere electrode with hierarchy |
| CN106848269A (en) * | 2017-04-26 | 2017-06-13 | 国家纳米科学中心 | A kind of three-dimensional conductive networking Si-C composite material and its preparation method and application |
| CN107275590A (en) * | 2017-05-19 | 2017-10-20 | 浙江大学 | A kind of porous Si-C composite material and its preparation method and application |
| CN108288707A (en) * | 2018-02-11 | 2018-07-17 | 合肥国轩高科动力能源有限公司 | Preparation method and application of micron-sized pomegranate-shaped silicon-carbon negative electrode material |
| CN109728288A (en) * | 2018-09-06 | 2019-05-07 | 长兴材料工业股份有限公司 | Si-C composite material and preparation method thereof, cathode of lithium battery and lithium battery |
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| CN106784661A (en) * | 2016-12-02 | 2017-05-31 | 黑龙江科技大学 | A kind of preparation method of the graphene/silicon porous microsphere electrode with hierarchy |
| CN106784661B (en) * | 2016-12-02 | 2019-05-21 | 陕西科技大学 | A kind of preparation method of the graphene/silicon porous microsphere electrode with hierarchy |
| CN106848269A (en) * | 2017-04-26 | 2017-06-13 | 国家纳米科学中心 | A kind of three-dimensional conductive networking Si-C composite material and its preparation method and application |
| CN106848269B (en) * | 2017-04-26 | 2018-10-23 | 北京乐华锂能科技有限公司 | A kind of three-dimensional conductive networking Si-C composite material and its preparation method and application |
| CN107275590A (en) * | 2017-05-19 | 2017-10-20 | 浙江大学 | A kind of porous Si-C composite material and its preparation method and application |
| CN108288707A (en) * | 2018-02-11 | 2018-07-17 | 合肥国轩高科动力能源有限公司 | Preparation method and application of micron-sized pomegranate-shaped silicon-carbon negative electrode material |
| CN109728288A (en) * | 2018-09-06 | 2019-05-07 | 长兴材料工业股份有限公司 | Si-C composite material and preparation method thereof, cathode of lithium battery and lithium battery |
| CN111370656A (en) * | 2018-12-26 | 2020-07-03 | 国家纳米科学中心 | Silicon-carbon composite material and preparation method and application thereof |
| CN111370656B (en) * | 2018-12-26 | 2021-12-17 | 国家纳米科学中心 | Silicon-carbon composite material and preparation method and application thereof |
| CN111640919A (en) * | 2020-05-14 | 2020-09-08 | 浙江金鹰新能源技术开发有限公司 | High-first-efficiency silicon-carbon negative electrode material, preparation method thereof and lithium ion battery |
| CN116477600A (en) * | 2023-03-16 | 2023-07-25 | 华南理工大学 | High specific capacity silicon-carbon negative electrode material and preparation method and application thereof |
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