CN106784717A - A kind of preparation method of nano silicon coated graphite negative material - Google Patents

A kind of preparation method of nano silicon coated graphite negative material Download PDF

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CN106784717A
CN106784717A CN201611250975.5A CN201611250975A CN106784717A CN 106784717 A CN106784717 A CN 106784717A CN 201611250975 A CN201611250975 A CN 201611250975A CN 106784717 A CN106784717 A CN 106784717A
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graphite
nano silicon
black
negative material
grey
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刘瑶
黄光艳
李闯
余冲
项朗
林定文
张文博
丁先红
舒方君
周环波
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Hubei Uee Energy Technology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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

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  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
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  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a kind of preparation method of nano silicon coated graphite negative material, first under agitation to certain Si:The graphite silicon compound mixed solution and dripping acid solution of C mol ratios, control pH, reaction temperature, the time of reaction system, the silica sol for obtaining, dry, obtain graphite silicic acid gel, graphite silicic acid gel is mixed with water again, is washed, filtered, dry graphite silicic acid gel, graphite silicic acid gel is thermally decomposed under vacuum, obtain nano silicon coated graphite negative material.The grain diameter of gained nano silicon coated graphite negative material is 1~35 μm, and it has specific discharge capacity and preferable cycle performance and high-rate characteristics higher higher.

Description

A kind of preparation method of nano silicon coated graphite negative material
Technical field
The present invention relates to field of lithium ion battery material, a kind of nano silicon coated graphite negative pole material is more particularly to The preparation method of material.A kind of nano silicon coated graphite negative material prepared by the present invention can serve as lithium ion battery Negative electrode active material, manufactures lithium ion battery.
Background technology
At present, the negative material typically graphite material that lithium ion battery is used.The phase of lithium ion battery negative material Research is closed also to be concentrated mainly on to the modified of native graphite, new CNT, Graphene, amorphous carbon and numerous metals Oxide etc..Wherein, graphite is the carbon negative pole material for being used for lithium ion battery earliest, and its good conductivity, crystallinity is high, with complete Whole layered crystal structure, insertion and the abjection of suitable lithium ion.But, graphite as lithium ion battery negative electrode active material Material, because the features such as its is nonpolar, density is low, mechanical strength is poor, except graphite capacity is relatively low, charge-discharge performance compared with Difference etc. is outside defect, during lithium ion battery negative electrode is manufactured graphite cathode also exist it is poor with the compatibility of water, point Divergence is low, poor processability, the deficiency such as production process graphite dust pollution production environment and equipment.
The material of " having similar to graphite laminate structure " that CNT is made up of the coaxial carbon plate layer of single or multiple lift. The sp of CNT2Hybrid structure and draw ratio high bring a series of excellent properties for it.This special microcosmic knot Structure causes that the insert depth of lithium ion is small, stroke is short and embedded location is more (pipe interior and interlayer gap, hole etc.), while because of carbon Nanotube conductive performance very well, with the conduction of preferable electronics and ion transport capacity, is suitable as lithium ion battery negative material. Therefore, CNT is used as lithium ion battery negative material, it is clear that than traditional graphite electrode advantageously.But using carbon nanometer Pipe there is also weak point directly as lithium ion battery negative material：1) irreversible capacity is larger first, first charge-discharge effect Rate is than relatively low；2) carbon nanometer tube negative pole lacks the voltage platform of stabilization；3) there is current potential hysteresis in CNT.Additionally, carbon The synthesis cost of nanotube is high.These all limit practical application of the CNT as lithium ion battery negative material.Stone Black alkene (Graphene) be one kind only by carbon atom with sp2Hybridized orbit constitutes the flat film of hexangle type lattice, that is, only One two-dimensional material of carbon atom thickness.Compared to other Carbon Materials such as CNT, Graphene has unique microstructure, this So that Graphene has larger specific surface area and cellular void structure, with storage lithium ability higher.Additionally, material is in itself With good chemical stability, high electron mobility and excellent mechanical property, it is had as electrode material and protrude Advantage.Similar with CNT, coulombic efficiency is low, charge and discharge platform is higher and circulates due to circulating first for pure grapheme material Less stable, synthesis cost are very high, commercial value shortcoming etc. defect, and the Carbon Materials of current commercialization can not be replaced directly to use Make lithium ion battery negative material.Metal oxide-carbon is (such as：SnO、VO2、TiO2、LixFe2O3、Li4Mn2O12、Li4Ti5O12Cover Carbon material etc.) material as lithium ion battery negative pole, due in organic electrolyte solution carbon surface formed can allow electronics and The freely through passivation layer of lithium ion, while this passivation layer ensure that electrode good cycle performance, can cause electrode tight The loss of the first charge-discharge irreversible capacity of weight, can even cause the structure change and poor electric contact of electrode interior sometimes. In addition, being likely to cause battery failure because of the decomposition of protective layer under high temperature or producing safety problem.
In order to improve the above-mentioned not enough or defect of lithium ion battery negative material, function admirable, high security are produced Lithium ion battery, those skilled in the relevant art mainly research and develop novel cathode material for lithium ion battery.Document " silicon monoxide/ Carbon/expanded graphite is used as lithium ion battery negative material [J] " (battery, 2016,46 (3)：121-124.) report：With poly- second Enol butyral is carbon source, in silicon monoxide (SiO) coated with carbon bed then compound with expanded graphite, prepares lithium ion battery The negative pole method of SiO/C/ exfoliated-graphite composites, it is said that：The 200mA/g multiplying powers of the SiO/C/ exfoliated-graphite composites The 100th reversible specific capacity of circulation of discharge and recharge is 545mAh/g.Document " self-supporting WS2The Static Spinning of/carbon fibre composite Silk is prepared and its as the application [J] of lithium ion battery negative material " (Science Bulletin, 2016,61 (8)：912) utilization is described Electrostatic spinning technique is prepared for one kind " two-dimentional WS2Nanometer sheet is uniformly embedded in carbon nano-fiber composite material ", document claims, the skill Composite membrane section bar material prepared by art does not need conductive agent, bonding agent, can be directly used as lithium ion battery negative, can be directly from Make flexible battery device.Document " preparation of jute base carbon fibre/MnO/C lithium ion battery negative materials and its chemical property [J] " (Chinese Journal of Inorganic Chemistry, 2016,32 (5)：811-817) describe and be with tossa, potassium permanganate and polymer pyrroles Raw material, the technology of " carbon fiber/MnO/C " lithium ion battery negative material is prepared through more numerous and diverse step.Carbon fiber/MnO/C Material has effective electron channel and the polynary cooperative effect on composition in structure, is showed as lithium cell cathode material Go out specific capacity higher, good cycle performance and high rate performance.The document does not provide secure lithium ion battery Practicable technological parameter and process conditions etc.." metatitanic acid high temperature solid-state method prepares lithium ion battery negative material point to document Spar Li4Ti5O12[J] " (electronic original part and material, 2016,35 (3)：19-21) report and synthesize " point crystalline substance with solid reaction process Stone-type Li4Ti5O12Negative material "." the spinel-type Li of document report4Ti5O12The first charge-discharge capacity of negative material " is 158.63mAh/g, (electric current) efficiency is 98.7%.Document " ZnFe2O4The preparation of lithium ion battery negative material and electrochemistry [J] can be studied " (Journal of Inorganic Materials, 2016,31 (1)：34-38) have studied with hydro-thermal-solid phase that ZnFe chlorides are raw material Reaction method prepares " ZnFe2O4The contents such as the technology and chemical property of negative material ".The ZnFe of document synthesis2O4Negative pole material Expect to be nanometer porous spherical particle, with reversible specific capacity and relatively stable cycle performance higher.
Additionally, document " preparation of uniform load nickel oxide nanoparticle porous hard carbon ball and its high performance lithium ion battery Negative material application [J] " (Acta PhySico-Chimica Sinica, 2015,31 (2)：268-276) describe it is a kind of using hydro-thermal method prepare lithium from The technology of sub- cell negative electrode material.It is said that under the composite 100mA/g current density charge conditions of document report synthesis, Initial charge specific capacity is 764mAh/g, and charge specific capacity is maintained at 777mAh/g after circulation in 100 weeks；800mA/g current densities Under charge condition, charging capacity 380mAh/g." zinc replaces to spinelle Li document2MnTi3O8Lithium ion battery negative material is micro- See the influence [J] of structure and chemical property " (non-ferrous metal engineering, 2015,5 (6)：1-6) synthesized with sol-gel process Li2MnTi3O8Aqueous precursor gel material, adds ZnAc2, zinc substitution is prepared to spinelle Li through high-temperature calcination2MnTi3O8Lithium from Sub- cell negative electrode material.Document claims：The zinc of synthesis replaces to spinelle Li2MnTi3O8Lithium ion battery negative material fills at 36 times Specific capacity after discharge cycles is respectively 199.4mAh/g and 260.2mAh/g.Document " lithium ion battery negative material Li4Ti5O12Synthesis and performance study [J] " (electrochemistry, 2015,21 (2)：181-186) describe with TiO2, lithium acetate for original Material, synthesis in solid state lithium ion battery negative Li4Ti5O12The method of material.Report synthesis Li4Ti5O1210C high magnifications put first Electric specific capacity reaches 143.0mAh/g." three-dimensional multistage hole class Graphene carries di-iron trioxide lithium ion battery negative material to document [J] " (electrochemistry, 2015,21 (1)：66-71), with synthetic technologys such as numerous and diverse ion exchange, liquid phase reactor, solid phase roastings, close Into and have studied three-dimensional porous Graphene and carry performance of the di-iron trioxide as lithium ion battery negative material.Document claims：Synthesis Fe2O3The first discharge specific capacity of -3D HPG materials is up to 1745mAh/g, and 50 times circulation specific capacity is maintained at 1095mAh/g. Document " multilevel hierarchy SnO2 nano flowers are used as high performance lithium ionic cell cathode material [J] " (Science Bulletin, 2015,60 (9)： 892-895) describe " flower-shape nano SnO2" negative material solvent-thermal method technology of preparing.Flower-shape nanometer prepared by the document SnO2The reversible capacity of negative material is 350.7mAh/g." lamellar titanosilicate compound is used as lithium ion battery negative for document Energy storage material [J] " (Chinese Journal of Inorganic Chemistry, 2015,31 (12)：2425-2431) have studied and use lamellar titanosilicate Na4Ti2Si8O22·4H2O (Na-JDF-L1) prepares lithium ion battery negative material through ion-exchange.It is main by by TiO2 It is incorporated into Li (Na)-JDF-L1, effectively improves the coulombic efficiency first and multiplying power discharging property of material.
There are substantial amounts of synthesis about silica, modified and application patent to disclose.Chinese patent (ZL200510064682.5, ZL 03105299.1) discloses " a kind of preparation method of nano silicon ", Chinese patent (ZL 02155203.7) is disclosed " composite nano silica/ferroferric oxide grain material and preparation method thereof ", and China is specially Sharp (application number 200610009601.4) discloses " method that nano silicon is prepared with rice hull ash ", Chinese patent (ZL 200410010304.2) " a kind of nano silicon dioxide particles preparation method ", Chinese patent (application number are disclosed 20081004251.0) " a kind of nano-silicon dioxide hollow sphere material and preparation method thereof ", Chinese patent (application number are disclosed 2006101300304.5) disclose " a kind of preparation method of hydrophobic nano-silica " etc..United States Patent (USP) " Light- emitting device having a thin insulating film made of nitrogen and silicon And an electrode made of conductive transparent oxide and silicon dioxide " are (specially Sharp application number：7,902,747,2011.8) disclose a kind of " with the thin dielectric membrane as manufactured by nitrogen and silicon and by conductive, transparent The light-emitting device of the electrode that oxide and silica are made ".Have no relevant nano silicon coated graphite negative material system Standby technology is disclosed or used.
The content of the invention
The purpose of the present invention is to there are provided a kind of preparation method of nano silicon coated graphite negative material, side The raw materials used abundance of method, technical equipment are relatively simple, easy, technological process is simple, production technology low cost, and preparation is received Rice coated with silica graphite cathode material, with the particle size distribution range (particle diameter distribution of modified graphite used by depending on wider With the preparation technology parameter of the covering amount of nano silicon and collosol and gel etc.), coated with silica amount is easily controlled, manufacture The features such as lithium ion battery negative electrode has good processing characteristics and fillibility higher, compacted density higher.
The present invention is realized by following technical solution：A kind of described nano silicon coated graphite negative material Preparation method, comprises the following steps：
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:5~1:20 graphite is (according to C12Graphite quality is calculated, below It is identical) and the mixing of the silicon compound aqueous solution that concentration is 0.1~6mol/L, stir 10~120 minutes, obtain graphite-silication and close Thing mixed solution；
Second step, stirred in room temperature (25~28 DEG C, same as below), with magnetic stirrer (magneton) or electric blender Under conditions of, to the acid solution that graphite-silicon compound mixed solution and dripping concentration is 0.2~10mol/L, control reaction system PH value be 2.5~5.5, continue stir 10~120 minutes, stand 2~24 hours, obtain grey or grey black or black stone Ink-silica sol；
3rd step, by graphite-silica sol under the conditions of 65~120 DEG C dry 4~24 hours, obtain grey or grey black Or black graphite-silicic acid gel；Graphite-silicic acid gel is mixed with the water that volume is graphite -2~5 times of Silica hydrogel volume, is stirred 10~120 minutes, wash with water graphite-silica sol to eluate be neutral (pH=6.8 or 7.0 or 7.2, as follows, slightly), Filtering, that is, obtain grey or grey black or black graphite-silicic acid gel powder；
4th step, graphite-silicic acid gel powder is placed in temperature programmed control vacuum Muffle furnace, with 1~10 DEG C per minute Heating rate is warming up to and is thermally decomposed under 350~750 DEG C, 0.1~0.01MPa vacuum conditions, is incubated 4~24h, naturally cools to Room temperature, that is, obtain grey or grey black or black nano coated with silica powdered graphite；
In order to be better achieved the present invention, described silicon compound is sodium metasilicate, potassium silicate, ammonium silicate are therein any Kind；
Described acid be hydrochloric acid, nitric acid, sulfuric acid or acetic acid it is therein any one；
Described water be natural water, running water, distilled water, redistilled water or deionized water it is therein any one.
The present invention compared with prior art, has the following advantages that and beneficial effect：
1st, the particle diameter distribution using a kind of nano silicon coated graphite negative material of present invention synthesis is wider, and main To depend on the preparation technology parameter of the particle diameter, coated with silica amount and collosol and gel of graphite material to be modified, silica Covering amount and cladding thickness it is easily controllable, and the nano silicon coated graphite negative material of easily controllable synthesis particle diameter (refer to：Embodiment and accompanying drawing)；
2nd, a kind of nano silicon coated graphite negative material prepared using the present invention, manufactured lithium ion battery With charging and discharging capacity higher and high-multiplying power discharge effect, highest specific discharge capacity reaches 523mAh/g (embodiment 5), does not wrap The highest specific discharge capacity for covering the graphite (hereinafter referred to as " comparative sample ") of nano silicon is only 304mAh/g；5C multiplying powers 300 times charge and discharge cycles amount conservation rate is up to 98.2%, and comparative sample is 70.1%；500 times charge and discharge cycles capacity is protected Holdup is up to 96.6% (embodiment 5), and comparative example is only 45.3% (accompanying drawing 12, accompanying drawing 13, accompanying drawing 14)；
3rd, a kind of nano silicon coated graphite negative material prepared using the present invention, because clad silica Density it is larger, and machinery is higher, physical and chemical stability preferably, relatively low with the density and easy characteristic phase for forming more fine powder Than, dispersion is easier in aqueous, with more preferable electrode slice processing characteristics, it is beneficial to improve cathode pole piece with electrolyte Compatibility, and then the pole piece quality that improves and performance of lithium ion battery, and significantly improve lithium ion battery production efficiency；
4th, a kind of nano silicon coated graphite negative material prepared using the present invention, is used in the appropriate bonding agent that reduces In the case of amount, pole piece dry linting, shedding phenomenon weaken significantly, and in lithium ion battery negative manufacturing process, it is right to effectively reduce Workshop environment causes dust pollution, the social benefit with good economic benefits and significant environmental benefit sum；
5th, the particle of the silica of a kind of nano silicon coated graphite negative material prepared using the present invention Footpath, thickness, the content of coated with silica layer etc. are easily controllable, can be according to different type lithium ion battery (rate lithiums Ion battery, capacity type lithium ion battery etc.) the need for, prepare that coated with silica amount is different, grain diameter is different, electrical property There is the nano silicon coated graphite negative material of different；
6th, using the present invention prepare a kind of nano silicon coated graphite material preparation process is flexible, equipment simple, Raw material are cheap, the comprehensive low production cost of material, it is easy to accomplish large-scale industrial production.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 1；
Fig. 2 is the XRD of nano silicon coated graphite negative material prepared by embodiment 1；
Fig. 3 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 2；
Fig. 4 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 3；
Fig. 5 is the XRD of nano silicon coated graphite negative material prepared by embodiment 3；
Fig. 6 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 4；
Fig. 7 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 5；
Fig. 8 is the XRD of nano silicon coated graphite negative material prepared by embodiment 5；
Fig. 9 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 6；
Figure 10 is the stereoscan photograph of nano silicon coated graphite negative material prepared by embodiment 7；
Figure 11 is the XRD of nano silicon coated graphite negative material prepared by embodiment 7；
Figure 12 is the highest specific capacity of each embodiment, 300 and 500 cyclic discharge capacity conservation rate comparison diagrams；
Figure 13 is exemplary embodiments and the charge and discharge cycles discharge capacity figure of comparative example 300；
Figure 14 is the charge and discharge cycles discharge capacity figure of exemplary embodiments (embodiment 5) 500；
Specific embodiment
With reference to the accompanying drawings and examples, the present invention is done and is further described in detail.
Embodiment 1:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:20 graphite and concentration is the ammonium silicate solution of 0.1mol/L Mixing, stirs 120 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, in room temperature (25 or 26 or 27 or 28 DEG C, same as below), with magnetic stirrer (magneton) or electric mixing Mix under conditions of machine stirring, to the acetum of graphite-ammonium silicate mixed solution and dripping 10mol/L concentration, control reactant The pH value of system is 5.5, continues to stir 120 minutes, stands 4 hours, obtains grey or black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 65 DEG C dry 24 hours, obtain black graphite-silicic acid gel, will Graphite-silicic acid gel and volume mix for the water of graphite -5 times of silica sol volume, stir 30 minutes, with natural water washing stone Ink-silica sol to eluate is neutral, filtering, that is, obtain black carbon-silicic acid gel powder；
4th step, graphite-silica sol powder is placed in temperature programmed control vacuum Muffle furnace, with 1 DEG C per minute of intensification Speed be warming up under 350 DEG C, 0.01MPa vacuum conditions thermally decompose, be incubated 4h, naturally cool to room temperature (25 or 26 or 27 or It is 28 DEG C, same as below), that is, obtain black nano coated with silica powdered graphite；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm (Fig. 1), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original Crystalline particle particle diameter is in 1~25nm (Fig. 2, SiO2Diffraction maximum half-peak breadth is calculated, same as below)；Nano silicon coated graphite The highest specific discharge capacity of negative material is 412mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 97.3%, 500 charge and discharge cycles capability retentions 92.2% (Figure 12).
Embodiment 2:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:18 graphite and concentration is the potassium silicate solution of 0.2mol/L Mixing, stirs 100 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, in room temperature, stirred with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon The sulfuric acid solution of sour potassium mixed solution and dripping 8mol/L concentration, it is 4.5 to control the pH value of reaction system, continues to stir 100 points Clock, stands 8 hours, obtains black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 85 DEG C dry 20 hours, obtain black graphite-silicic acid gel；Will Graphite-silicic acid gel and volume mix for the running water of graphite -4 times of silica sol volume, stir 30 minutes, with originally water washing Graphite-silica sol to eluate is neutral, filtering, that is, obtain black graphite-silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute 5 DEG C of heating rate is warming up to and is thermally decomposed under 450 DEG C, 0.02MPa vacuum conditions, is incubated 8h, naturally cools to room temperature, obtains final product To black nano coated with silica powdered graphite；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm (Fig. 3), average grain diameter is about 20 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original Crystalline particle particle diameter is in 1~25nm；The highest specific discharge capacity of nano silicon coated graphite negative material is 438mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 98.1%, 500 charge and discharge cycles capability retentions 94.4% (Figure 12).
Embodiment 3:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:15 graphite and concentration is the sodium silicate solution of 0.5mol/L Mixing, stirs 80 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, in room temperature, stirred with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon Sour sodium mixed solution and dripping concentration is the sulfuric acid solution of 6mol/L, controls the pH value of reaction system to be about 3.5, continues to stir 80 minutes, 12 hours are stood, obtain grey black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 100 DEG C dry 16 hours, obtain grey or black graphite-silicic acid Gel；Graphite-silicic acid gel is mixed with the distilled water water that volume is graphite -3 times of silica sol volume, 80 minutes is stirred, is used Distilled water graphite water-silica sol to eluate is neutral, filtering, that is, obtain grey or black graphite-silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute 10 DEG C of heating rate is warming up to and is thermally decomposed under 550 DEG C, 0.04MPa vacuum conditions, is incubated 12h, naturally cools to room temperature, i.e., Obtain grey black nano silicon coated graphite powder；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm (Fig. 4), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original Crystalline particle particle diameter is at 1~5nm (Fig. 5)；The highest specific discharge capacity of nano silicon coated graphite negative material is 464mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 95.3%, 500 charge and discharge cycles capacity Conservation rate 92.7% (Figure 12).
Embodiment 4:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:12.5 graphite and concentration is the sodium silicate solution of 1mol/L Mixing, stirs 60 minutes, obtains graphite-sodium metasilicate mixed solution；
Second step, stirred in room temperature and with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon Sour sodium mixed solution and dripping concentration is the hydrochloric acid solution of 4mol/L, and it is 2.5 to control the pH value of reaction system, continues to stir 60 Minute, 16 hours are stood, obtain grey or black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 12 hours, obtain grey black graphite-silicic acid coagulate Glue；Graphite-silicic acid gel and volume are mixed for the redistilled water water of graphite -5 times of silicic acid gel volume, stir 60 minutes, It is neutral, filtering with redistilled water water washing graphite-silica sol to eluate, that is, obtains grey black graphite-silica sol Powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute 1~10 DEG C of heating rate is warming up to and is thermally decomposed under 550 DEG C, 0.06MPa vacuum conditions, is incubated 16h, naturally cools to room Temperature, that is, obtain grey black nano silicon coated graphite powder.
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite material is the polymorphs such as irregular spheroid, barred body, and its particle size range is between 1~25 μm (Fig. 6), average grain diameter is about 10 μm, and coated with silica layer crystal body is amorphous nano silicon, silica it is original Crystalline particle particle diameter is in 1~5nm；The highest specific discharge capacity of nano silicon coated graphite negative material is 504mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 96.6%, 500 charge and discharge cycles capability retentions 991.5% (Figure 12).
Embodiment 5:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:10 graphite and concentration is mixed for the sodium silicate solution of 2mol/L Close, stir 40 minutes, obtain graphite-sodium metasilicate mixed solution；
Second step, in room temperature, stirred with magnetic stirrer (magneton) or electric blender under conditions of, to graphite-silicon Sour sodium mixed solution and dripping concentration is the hydrochloric acid solution of 2mol/L, and it is 3.5 to control the pH value of reaction system, continues to stir 40 points Clock, stands 12 hours, obtains grey black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 8 hours, obtain grey or black graphite-silicic acid Gel (hereinafter referred to as Silica hydrogel)；By graphite-silicic acid gel with volume for the distilled water water of graphite -2 times of silica sol volume is mixed Close, stirring 30 minutes, be neutral, filtering with distilled water graphite water-silica sol to eluate, that is, obtain grey black graphite- Silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute 2 DEG C of heating rate is warming up to and is thermally decomposed under 650 DEG C, 0.08MPa vacuum conditions, is incubated 20h, naturally cools to room temperature, i.e., Obtain grey black nano silicon coated graphite powder；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite material is the polymorphs such as irregular particle, barred body, piece shape, and its particle size range is at 1~30 μm Between (Fig. 7), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, silica Initial crystalline grain diameter is at 1~3nm (Fig. 8)；The highest specific discharge capacity of nano silicon coated graphite negative material is 523mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 95.2%, 500 charge and discharge cycles capacity Conservation rate 92.7% (Figure 12, Figure 13, Figure 14).
Embodiment 6:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:7.5 graphite and concentration is mixed for the sodium silicate solution of 4mol/L Close, stir 20 minutes, obtain graphite-sodium metasilicate mixed solution；
Second step, room temperature, magnetic stirrer (magneton) or electric blender stirring under conditions of, to graphite-silicic acid The hydrochloric acid solution of sodium mixed solution and dripping 2mol/L concentration, it is 3.5 to control the pH value of reaction system, continues to stir 20 points Clock, stands 24 hours, obtains grey graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 2 hours, obtain grey graphite-silicic acid gel；Will Graphite-silicic acid gel mixes with the deionized water that volume is graphite -2 times of silica sol volume, stirs 120 minutes, uses deionization Water washing graphite-silica sol to eluate is neutral, filtering, that is, obtain grey graphite-silica sol powder；
4th step, grey or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with per minute 10 DEG C of heating rate is warming up to and is thermally decomposed under 350 DEG C, 0.1MPa vacuum conditions, is incubated 8h, naturally cools to room temperature, obtains final product To grey or black nano coated with silica powdered graphite；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite negative material is the polymorph such as irregular spheroid, barred body, its particle size range 1~20 μm it Between (Fig. 9), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, the original of silica Beginning, crystalline particle particle diameter was in 1~5nm；The highest specific discharge capacity of nano silicon coated graphite negative material is 481mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 97.8%, 500 charge and discharge cycles capability retentions 95.6% (Figure 12).
Embodiment 7:
A kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:5 graphite and concentration is mixed for the sodium silicate solution of 6mol/L Close, stir 10 minutes, obtain graphite-potassium silicate mixed solution；
Second step, room temperature, magnetic stirrer (magneton) or electric blender stirring under conditions of, to graphite-silicic acid The hydrochloric acid solution of sodium mixed solution and dripping 10mol/L concentration, it is 3.5 to control the pH value of reaction system, continues to stir 10 minutes, 24 hours are stood, grey graphite-silica sol is obtained；
3rd step, by graphite-silica sol under the conditions of 120 DEG C dry 4 hours, obtain grey graphite-silicic acid gel；Will Graphite-silicic acid gel mixes with the distilled water water that volume is graphite -5 times of silica sol volume, stirs 10 minutes, is washed with distillation It is neutral, filtering to wash graphite-silica sol to eluate, that is, obtain grey graphite-silica sol powder；
4th step, grey graphite-silica sol powder is placed in temperature programmed control vacuum Muffle furnace, with 10 DEG C per minute Heating rate is warming up to and is thermally decomposed under 750 DEG C, 0.1MPa vacuum conditions, is incubated 24h, naturally cools to room temperature, that is, obtain ash Color nano silicon coated graphite powder；
Pattern, particle diameter and the crystal for preparing nano silicon coated graphite negative material are determined with SEM, XRD technology Structure, using the nano silicon coated graphite negative material of preparation as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Prepare gained nanometer titanium dioxide The pattern of silicon coated graphite negative material is the polymorph such as irregular spheroid, barred body, its particle size range 1~35 μm it Between (Figure 10), average grain diameter is about 15 μm, and coated with silica layer crystal body is amorphous nano silicon, the original of silica Beginning crystalline particle particle diameter is at 1~3nm (Figure 11)；The highest specific discharge capacity of nano silicon coated graphite negative material is 433mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capability retentions 96.7%, 500 charge and discharge cycles capacity Conservation rate 94.1% (Figure 12).
Comparative example 8:
Using the graphite cathode material of uncoated nano silicon as negative electrode active material, manufacture cathode pole piece assembling is held The lithium ion battery for 1000mAh is measured, the charge and discharge circulation that lithium ion battery is determined under the conditions of 0.2C, 5C charge-discharge magnification is electrical Specific discharge capacity that, can prepare nano silicon coated graphite negative material etc., as a result shows：Uncoated nano silicon Graphite cathode material highest specific discharge capacity be 304mAh/g (0.2C multiplying powers), 5C multiplying powers, 300 charge and discharge cycles capacity Conservation rate 70.1%, 500 charge and discharge cycles capability retentions 45.3% (accompanying drawing 12).
As described above, you can preferably realize the present invention.

Claims (1)

1. a kind of preparation method of nano silicon coated graphite negative material, its step is：
The first step, silicon, carbon mol ratio Si will be contained:C is 1:5~1:20 graphite and concentration is that the silication of 0.1~6mol/L is closed The thing aqueous solution mixes, and stirs 10~120 minutes, obtains graphite-silicon compound mixed aqueous solution；
Second step, in room temperature, stirred with magnetic stirrer or electric blender under conditions of, mix to graphite-silicon compound The acid solution that concentration is 0.1~10mol/L is added dropwise in solution, it is 2.5~5.5 to control the pH value of reaction system, continues to stir 10 ~120 minutes, 4~24 hours are stood, obtain grey or grey black or black graphite-silica sol；
3rd step, by graphite-silica sol under the conditions of 65~120 DEG C dry 2~24 hours, obtain grey or grey black or black Colored stone ink-silicic acid gel；Graphite-silicic acid gel and volume are mixed for the water of carbon -2~5 times of silicic acid gel volume, stir 10~ 120 minutes, to wash graphite-silica sol to eluate with water be neutral, filtering, obtain grey or grey black or black graphite- Silica sol powder；
4th step, grey or grey black or black graphite-silica sol powder are placed in temperature programmed control vacuum Muffle furnace, with every Minute 1~10 DEG C of heating rate is warming up in 350~750 DEG C, 4~24h of insulation, naturally cools to room temperature, 0.1~ Thermally decomposed under 0.01MPa vacuum conditions, obtain grey or grey black or black nano coated with silica powdered graphite；
Described silicon compound be sodium metasilicate, potassium silicate, ammonium silicate it is therein any one；
Described acid be hydrochloric acid, nitric acid, sulfuric acid or acetic acid it is therein any one；
Described water be natural water, running water, distilled water, redistilled water or deionized water it is therein any one.
CN201611250975.5A 2016-12-29 2016-12-29 A kind of preparation method of nano silicon coated graphite negative material Pending CN106784717A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109524630A (en) * 2017-09-20 2019-03-26 上海杉杉科技有限公司 A kind of preparation method of cladded type composite negative pole material
CN111320868A (en) * 2018-12-17 2020-06-23 杜邦聚合物有限公司 Polymer composition with high dielectric constant and low dielectric loss

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210118A (en) * 2006-12-29 2008-07-02 比亚迪股份有限公司 Method for preparing carbon coating graphite/silicon oxide composite material
CN103515582A (en) * 2013-10-10 2014-01-15 中国海洋石油总公司 Preparation method of lithium ion battery silicon-carbon composite cathode material
CN104091952A (en) * 2014-07-24 2014-10-08 常州大学 Novel negative electrode material for lithium ion battery and preparation method of negative electrode material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101210118A (en) * 2006-12-29 2008-07-02 比亚迪股份有限公司 Method for preparing carbon coating graphite/silicon oxide composite material
CN103515582A (en) * 2013-10-10 2014-01-15 中国海洋石油总公司 Preparation method of lithium ion battery silicon-carbon composite cathode material
CN104091952A (en) * 2014-07-24 2014-10-08 常州大学 Novel negative electrode material for lithium ion battery and preparation method of negative electrode material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109524630A (en) * 2017-09-20 2019-03-26 上海杉杉科技有限公司 A kind of preparation method of cladded type composite negative pole material
CN111320868A (en) * 2018-12-17 2020-06-23 杜邦聚合物有限公司 Polymer composition with high dielectric constant and low dielectric loss
WO2020131212A1 (en) * 2018-12-17 2020-06-25 Dupont Polymers, Incorporated Polymeric compositions with high dielectric constant and low dielectric loss
CN113614163A (en) * 2018-12-17 2021-11-05 杜邦聚合物公司 Polymer composition with high dielectric constant and low dielectric loss
CN111320868B (en) * 2018-12-17 2023-02-28 杜邦聚合物有限公司 Polymer composition with high dielectric constant and low dielectric loss
CN113614163B (en) * 2018-12-17 2023-06-16 杜邦聚合物公司 Polymer composition with high dielectric constant and low dielectric loss

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