CN107512718B - A kind of preparation method and application of the nm-class silicon carbide material of high metal content - Google Patents

A kind of preparation method and application of the nm-class silicon carbide material of high metal content Download PDF

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CN107512718B
CN107512718B CN201710665016.8A CN201710665016A CN107512718B CN 107512718 B CN107512718 B CN 107512718B CN 201710665016 A CN201710665016 A CN 201710665016A CN 107512718 B CN107512718 B CN 107512718B
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silicon carbide
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metallic
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CN107512718A (en
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张洪涛
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湖北工业大学
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
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    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
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    • C01P2002/52Solid solutions containing elements as dopants
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    • C01INORGANIC CHEMISTRY
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
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    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/40Electric properties

Abstract

The present invention provides a kind of preparation method of the nm-class silicon carbide material of high metal content, and electrode, the full silicon carbide lithium secondary battery of the nm-class silicon carbide material preparation using the high metal content.The raw materials used preparation method includes amorphism silicon powder, polysiloxanes, lithiumation polyacetylene and metal mixed powder, the metal mixed powder is mixed by metallic lithium powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder, metallic titanium powder, and dielectric barrier discharge plasma technique and high energy ultrafast laser technique are used simultaneously, tenor is high in obtained rice carbofrax material;The service life of full silicon carbide lithium secondary battery made of the electrode assembling prepared as the nm-class silicon carbide material of the high metal content is long, capacity is high, good cycle, coulombic efficiency reaches 99.9% for the first time for it, discharge platform is 4.1~3.5V, specific capacity reaches 2450mAh/g, discharge energy density reaches 1600~2000Wh/kg, power density reaches 1600~2000W/kg, and cycle period can achieve 20000 times.

Description

A kind of preparation method and application of the nm-class silicon carbide material of high metal content

Technical field

The present invention relates to a kind of nano materials, and in particular to a kind of preparation side of the nm-class silicon carbide material of high metal content Method and application, belong to field of new energy technologies.

Background technique

The haze as caused by fuel-engined vehicle tail gas seriously damages people's health.Abatement haze is using new at all The energy, such as electric vehicle drive in city, power plant is renewable non-combustible using solar power generation and wind-power electricity generation, hydroelectric generation etc. Coal technology obtains clean energy resource.This show new energy technology rely existing necessary condition first is that the storage of energy and transporting. Present energy storage technology locks into battery life and capacity, and Prospect of EVS Powered with Batteries also needs to consider safety problem.This several The existing secondary cell of technical indicator is not able to satisfy.There are the longevity for the electrode materials such as organic polymer, silicon alloy base and lithium titanate Order short or low energy density defect, exploitation novel long-life, high specific energy and high security electrode material and its lithium secondary battery As the task of top priority.

The positive and negative pole material of lithium secondary battery is now sold in market, such as LiFePO4, lithium nickel manganese oxide, cobalt acid lithium or other ternary The capacity of conjunction object electrode is low, cycle period is short, research and development are at high cost.Chinese invention patent (application number: 201310523769.7, Shen Please day: 2013.10.30) a kind of High-performance lithium battery lithium titanate negative electrode material and preparation method thereof, the high-performance lithium battery metatitanic acid Lithium titanate cathode material is made from the following raw materials in parts by weight: lithium titanate 400, graphite 3-4, copper nanoparticle 2-3, nanometer aluminium powder 1-2, Neopelex 2-3, modified silver powder 4-5, appropriate amount of water;The modified silver powder is made from the following raw materials in parts by weight: silver Powder 100, nano-sized carbon 1-2, tapioca 1-2, bauxite 2-3, diatomite 2-3, methyltriethoxysilane 1-2, silicon carbide 2- 3, aluminium nitride 1-2, ZnO1-2, Nb2O51-2.Using the battery of the lithium titanate anode material, initial charge specific capacity only > 175mAh/g, specific discharge capacity only > 160mAh/g, so the capacity of electrode is very low.

It has been investigated that volume expansion in charge and discharge process can be reduced using the nano-meter characteristic of material and shunk to electrode The influence of structure, to improve cycle performance.Practical application shows that the effective use of nano-meter characteristic can improve certain negative electrode materials Cycle performance, but can't realize large-scale industrial production.

Nanometer silicon carbide is the material of a kind of novel high-strength, high tenacity, has excellent mechanics and electric property.With it Unlike its substance, silicon carbide body material will not generate storage lithium phenomenon, and its nano material can be with this is because nanometer ruler The silicon carbide of degree is that have new property, and atomicity of the naked leakage in surface is more, and surface dangling bonds ratio accounts for bigger degree, Reduce chemical bond energy in nanoscale, lattice can elastic plastic strain, lithium ion can be migrated by diffusion admittance, diffusion coefficient Become larger, compared with lattice is not easy the body material silicon carbide of deformation, nanometer silicon carbide has a possibility that embedding lithium, and it is living to become electrochemistry Property material, thus lithium ion battery negative material can be used for.But silicon carbide doped is extremely difficult, and impurity is not easily accessible lattice, institute To be adulterated using specially treated technology, it is a problem to be solved that especially the metal of nanoscale, which adequately adulterates,.Especially It is that metal-doped technique is very complicated, and effect is also undesirable.

Nanometer silicon carbide obtains the nanometer silicon carbide containing metallic element because being doped with the metallic element of single atom, specifically Refer to that the silicon carbide containing metallic element for having at least unidimensional scale within 0.5~100nm, crystal chemistry structural formula are (SixMey)C1-x-y, wherein x and y is atomic weight percent, 0 < x < 1 and 0 < y < 1, and x+y < 1, Me are entered in silicon carbide lattice Metallic element, for example, the elements such as Li, Be, Mg, Al, Cs, Ti, Ag, Au, Pd and group of the lanthanides and actinium series rare earth;If Me is Referred to as nanometer silicon carbide containing lithium or nano-sized carbon lithiumation silicon when Li metallic element and when content is more than about 10%.It should be noted that Si and Me is substituted for each other as an element and puts together in structural chemical formula, is intended merely to facilitate expression structure chemical formula, In fact, the carbon of the lattice lattice point in nanometer silicon carbide crystal can also be replaced simultaneously into the metallic element in silicon carbide lattice Element, however, elecrtonegativity is high, and substituted probability is small since carbon atom radius is small, so it is same that silicon and metallic element are placed on class matter As substituted major part.It is of course also possible to express scale in the carborundum crystals of the doped metallic elements of 0.5~100nm, Crystal chemistry structural formula is Six(Cm Lin Mgp)1-x, 0 < x < 1,0 < m < 1,0 < n < 1,0 < p < 1 is the weight hundred of each element respectively Divide ratio, and m+n+p+x=1.

In view of this, the present invention proposes a kind of preparation method and application of the nm-class silicon carbide material of high metal content, with It solves the above problems.

Summary of the invention

It is an object of the invention to overcome the shortcomings of existing product, a kind of nm-class silicon carbide material of high metal content is provided Preparation method and application, metal element content is high in the nm-class silicon carbide material of high metal content prepared by the present invention, The ratio of middle metal elemental lithium is apparently higher than the ratio of other metals;By dielectric barrier discharge plasma work in preparation method Skill and high energy ultrafast laser technique combine, and the nanometer silicon carbide degree of purity of obtained high metal content is high, are single object phase; Prepared full silicon carbide lithium secondary battery has the advantages that the service life is long, specific capacity is high, energy density is high and stable cycle performance.

In order to achieve the above object, the technical scheme adopted by the invention is that: a kind of nanometer silicon carbide of high metal content Material, the content of metallic element accounts for the 0.1~20% of the nm-class silicon carbide material weight percent of the high metal content, described Metal includes elemental lithium, magnesium elements, aluminium element, beryllium element and titanium elements, and the content ratio of metal elemental lithium is apparently higher than it His metallic element;The crystal habit of the nm-class silicon carbide material of the high metal content includes in crystalline state, quasi-crystalline state and amorphous state It is one or more.

A kind of preparation method of the nm-class silicon carbide material of high metal content, comprising the following steps:

It (1) is reaction starting material, institute with amorphism silicon powder, polysiloxanes, lithiumation polyacetylene and metal mixed powder Metal mixed powder is stated to be mixed by metallic lithium powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder, metallic titanium powder;

(2) prepared reaction starting material is uniformly mixed, then dries, is finally pressed into disk;

(3) multiple medium blocking discharge electrodes are set in reaction vacuum chamber, and the disk is put in dielectric impedance and is put Between electrode, multi rack laser is uniformly arranged outside reaction vacuum chamber;

(4) vacuum chamber will be reacted, will be powered, dielectric barrier discharge generates plasma, laser emits laser vapour Change disk, stands 72h.

Further, the nm-class silicon carbide material of the high metal content is made of the raw material of following weight ratio: amorphous carbon SiClx powder 0.1~2%, polysiloxanes 45~54.5%, lithiumation polyacetylene 30~45% and metal mixed powder 0.4~23%.

Further, the metal mixed powder includes the component of following weight ratio: the metallic lithium powder of surfaces nitrided processing 90~99%, metallic aluminium powder 0.5~3%, metallic beryllium powder 0.1~3%, metal magnesium powder 0.2~2%, metallic titanium powder 0.2~2%.

Further, the disk is placed in the dish type graphite boat on reaction chamber central turnplate deck in step (3), Medium blocking discharge electrode is set at the both ends of at least one diameter of reaction chamber inscribed circle, the disk is located at two dielectric impedances Among discharge electrode;The medium blocking discharge electrode is high-frequency and high-voltage electrode, and is curved surface tiles, curvature and reaction chamber wall Curvature it is consistent.

Further, medium blocking discharge electrode described in the step (4) and example boat are in same level, described Medium blocking discharge electrode is multilayered structure, and one layer close to disk is tungsten metal mesh, and one layer close to reaction chamber wall is gold Belong to electrode, is to gather inclined tetrafluoroethene between tungsten metal mesh and metal electrode, the metal electrode gathers inclined tetrafluoroethene, tungsten metal Net with a thickness of 1~3cm, be divided into 1~5cm between both adjacent.

Further, the laser be all solid state ti sapphire laser, transmitting laser wavelength be 460nm and 540nm, laser gun axis line passes through deck center, and forms 30 ° of angles with deck surface.

Further, before step (4) vacuumizes, one piece of clean stainless steel plate is set in a vacuum chamber and is generated for collecting Reaction chamber is then vacuumized and reaches 1mTorr by object.

Further, the power supply of medium blocking discharge electrode is opened, discharges and generates plasma, after 5min, opens laser Device power supply emits ultrashort pulse, disk vaporization.

A kind of electrode, height prepared by the preparation method of the nm-class silicon carbide material comprising above-described high metal content The nanometer silicon carbide active material of tenor.

A kind of full silicon carbide lithium secondary battery, the anode and cathode of the battery are above-mentioned electrode, and anode and cathode Collector it is different;The anode and cathode are separated by Celgard polymer film, and inject electrolyte.

Further, the electrolyte be include ethylene carbonate, propene carbonate, methyl propyl carbonate, dipropyl carbonate, The 1M electrolyte of LiPF6;Can choose ethylene carbonate: propene carbonate: methyl propyl carbonate: dipropyl carbonate: LiPF6's matches Than for 2:2:2:1:1.

Further, the coulombic efficiency for the first time of the battery reaches 99.9%, and discharge platform is 4.1~3.5V, and specific capacity reaches To 2450mAh/g, discharge energy density reaches 1600~2000Wh/kg, and power density reaches 1800~2000W/kg, circulating cycle Phase can achieve 20000 times.

Nanometer silicon carbide is difficult to scale synthesis, the high nanometer silicon carbide containing amount of metal under general condition and is more difficult to scale Synthesis.The solid phase impurity except nanometer silicon carbide generally can be all generated, the nanometer silicon carbide for synthesizing single object phase must react The ingredient of object activates and can have nucleation stage to have enough energy supplies continuously to grow silicon carbide;Continuous growth refers to one herein The growth of the nanometer silicon carbide line of dimension state.Dielectric barrier discharge plasma technique and high energy ultrafast laser are combined, transported In the preparation process for using the nanometer silicon carbide of doping metals, the content of metal in nanometer silicon carbide can be significantly improved and can be protected Hold high-purity silicon carbide object phase.

Dielectric barrier discharge plasma is the condition of reactant ingredient activation, and generating nanometer silicon carbide is to need Atomic group or cluster are formed by fierce collision on the basis of each ingredient activation, at this moment silicon carbide nucleation stage occurs, anti- Each atomic group of object or cluster or silicon carbide core is answered to absorb the huge energy of laser, at this time nanometer silicon carbide core is in nucleus of the seed Guidance issue and be born from tissue growth, sufficiently receive metal activation atom, metallic atom occur and is evenly distributed on nanometer silicon carbide In lattice, the nanometer silicon carbide product of high metal content is generated.The fundamental of this reaction condition is dielectric impedance plasma The generation of body, for granule since difference in dielectric constant, surface discharge plasma can divide granule, this is that reactant activated Journey, the critical state that granule surface atom flies out, this process are also embodied by granule and attenuate, and are 0.1~70nm magnitude, this When under the effect of the laser, these reactive absorption laser energies, gasify for elementide or carbon atom and silicon atom composition it is micro- Subject plasma collides during flight again for core, such pyrene or cluster, by karyogenesis nanometer silicon carbide crystal.And Laser is during exciting activating substance, the electricity that fully inspires each simple substance HI high impact shearing force, electromagnetic force and pressure The collisions such as son, atom, ion and atomic group generate recombination and combine, and generate new object phase.Laser technology has Material growth Preferable effect.Past carries out ablation with laser from crystalline material, and gasification generates the nano particle of respective substance, received The preparation effect of metrical scale material is relatively good.However, for transparent or semitransparent body material, since continuous laser makes material gasify It is ineffective, it is not easy to produce nano material.So selection reactant feed, and binding medium barrier discharge plasma technique Gas is carried out for transparent, translucent, opaque granule or strong scattering granular powder with the ultrafast pulsed laser of high-energy density Change and generate strong energy converging in the meantime, infusibility substance can be synthesized, for example, silicon carbide powder.For silicon carbide, Because between silicon atom and carbon atom being covalent bond, other metallic atom diffusion lengths are short, and it is big that energy is migrated in lattice.And it adopts Metallic atom may make to be retained on lattice lattice point with this Laser Transient synthesizing silicon carbide.Make metal in this reaction process Element doping is a kind of feasible technology in silicon carbide lattice.

The beneficial effects of the present invention are:

(1) during preparing the nanometer silicon carbide of high metal content, by dielectric barrier discharge plasma technique and High energy ultrafast laser combines, and provides a kind of new direction to prepare the nm-class silicon carbide material of doping metals;And this method The nanometer silicon carbide degree of purity of obtained high metal content is high, is single object phase;

(2) it is had the following advantages that using nm-class silicon carbide material prepared by preparation method of the present invention, a: metal Content is high, reaches as high as the 20% of material total weight, wherein the ratio of metal elemental lithium is apparently higher than the ratio of other metals;B: The proportion of metallic element, adjusts the content of metallic element in nm-class silicon carbide material in changeable reactant;C: there is storage lithium effect It answers, can be used as electrode material and for assembled battery;

(3) the full silicon carbide lithium secondary battery prepared by the present invention with include the high metal content nanometer silicon carbide The electrode of material does anode and cathode, but anode is different with the collector of cathode, which has service life length, specific capacity height, energy The advantages of metric density height and stable cycle performance, cycle-index is up to 20000 times or more.

Detailed description of the invention

Fig. 1 is the scanning electron microscope image of the nanometer silicon carbide of high metal content prepared by the present invention;

Fig. 2 is the X-ray diffractogram of the nanometer silicon carbide of high metal content prepared by the present invention;

Fig. 3 is that the 1st time~50 times cycle period-capacity of positive plate-lithium half-cell-coulombic efficiency prepared by the present invention is special Property figure;

Fig. 4 is positive plate-charging/discharging voltage-Capacity Plan of lithium half-cell 1~50 time prepared by the present invention;

Fig. 5 is the 1st~8000 charging/discharging voltage-Capacity Plan of full silicon carbide lithium secondary battery prepared by the present invention;

Fig. 6 is the 1st~50 charging/discharging voltage-Capacity Plan of full silicon carbide lithium secondary battery prepared by the present invention;

Fig. 7 is full silicon carbide lithium secondary battery energy density-cycle diagram prepared by the present invention;

Fig. 8 is the nanometer silicon carbide cell configuration figure of high metal content prepared by the present invention.

Specific embodiment

In order to better understand the present invention, with reference to the accompanying drawing with the embodiment content that the present invention is furture elucidated, but this The content of invention is not limited solely to the following examples.

A kind of nm-class silicon carbide material of high metal content, the content of metallic element account for the nano-sized carbon of the high metal content The 0.1~20% of silicon nitride material weight percent, the metal include elemental lithium, magnesium elements, aluminium element, beryllium element and titanium member Element, and the content ratio of metal elemental lithium is apparently higher than other metallic elements;The nm-class silicon carbide material of the high metal content External morphology include crystalline state, quasi-crystalline state or amorphous state.

The specific preparation method of the nm-class silicon carbide material of the high metal content, comprising the following steps:

(1) prepared by metal mixed powder: in an inert atmosphere, by weight 90~99%:0.5~3%:0.1~3%: 0.2~2%:0.2~2% weighs metallic lithium powder, metallic aluminium powder, metallic beryllium powder, the metal magnesium powder, gold that nitrogen treatment is passed through on surface Belong to titanium valve, total 500g;The average diameter of the powder particle is 0.5~5um.The inert gas can be N2, Kr, He etc. it is common Inert gas;

(2) amorphism silicon powder is weighed by weight 0.1~2%:45~54.5%:30~45%:0.4~23%, gather Siloxanes, lithiumation polyacetylene, metal mixed powder, total 1200g;The average diameter of the powder particle is 0.5~5um;

(3) step (2) resulting material is put into stainless steel mixer, addition 300ml dehydrated alcohol, mechanical stirring 48h, It is uniformly mixed, fills mold set;

(4) by step (3) mold and mold cover in 90 DEG C of vacuum oven, dry 12h, take out;

(5) step (4) treated material is used on Kun press pressure 40MPa, is pressed into 2~3mm of thickness, diameter 2 The size and shape of the disk of~5cm, the disk can also be changed according to actual needs, become larger or become smaller, shape is The regular shapes such as polygon, but preferred disk.The quantity of disk can be determined according to actual needs, can for tens or Person several hundred;

(6) disk is placed in the dish type graphite boat on reaction chamber central turnplate deck, deck distance reaction Room bottom 10cm, vacuum chamber close to the position of top (such as 1.9m or other suitable height) be arranged one piece it is clean stainless For steel plate for collecting product, the stainless steel plate can be round, rectangular or other regular shapes;In reaction chamber inscribed circle The both ends of two perpendicular diameters two pairs of dielectric barrier electrodes are set, the dielectric barrier electrode and example boat are in same level Face, disk are located at the center of two pairs of dielectric barrier electrodes;

The dielectric barrier electrode is high-frequency and high-voltage electrode, and is curved surface tiles, the curvature one of curvature and reaction chamber wall It causes, watt projected area can be 8 × 8cm2Or 10 × 10cm2;The source nominal voltage of receiving electrode is 1~50kV, frequency 1~ 30kHz synchronizes adjustable;Dielectric barrier electrode is multilayered structure, and one layer close to disk is tungsten metal mesh, close to reaction chamber wall One layer be metal electrode, be to gather inclined tetrafluoroethene between tungsten metal mesh and metal electrode, the metal electrode gathers inclined tetrafluoro second Alkene, tungsten metal mesh with a thickness of 1~3cm, be divided into 1~5cm between both adjacent;

(7) reaction chamber is vacuumized and reaches 1mTorr, three frame high energy are uniformly arranged in the same level outside reaction chamber Ultrafast laser, the high energy ultrafast laser are all solid state ti sapphire laser, can launch wavelength be 460nm and 540nm Laser, laser gun axis line passes through deck center, and forms 30 ° of angles with deck surface;

(8) power supply for opening medium blocking discharge electrode discharges and generates plasma, and after 5min, it is ultrafast sharp to open high energy Light device power supply emits ultrashort pulse, and the duration of the pulse is 14fs, and energy density reaches 1018W/cm2, disk vaporization steaming Hair generates flue dust, while specimen holder carries out 360 ° of horizontal rotations, and laser can scan back and forth at example boat center to radius tip Sample, comprehensive scanning is until disk whole vaporization;

(9) stop laser scanning and dielectric barrier discharge, after standing 72 hours, take out stainless steel plate, surface deposits The as Neon SiC powder of high metal content.

Embodiment one

Raw materials used and its weight ratio are as follows: amorphism silicon powder 0.1%, polysiloxanes 54.5%, lithiumation polyacetylene 45% With metal mixed powder 0.4%, wherein metallic lithium powder in metal mixed powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder and The weight ratio of metallic titanium powder is 90:3:2.5:2.5:2, and the nm-class silicon carbide material preparation method of the high metal content is same as above.

Embodiment two

Amorphism silicon powder 0.5%, polysiloxanes 51%, lithiumation polyacetylene 40% and metal mixed powder 8.5%, In, metallic lithium powder in metal mixed powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder and metallic titanium powder weight ratio be 94: The nm-class silicon carbide material preparation method of 2.5:2:0.8:0.7, the high metal content are same as above.

Embodiment three

Amorphism silicon powder 1%, polysiloxanes 48%, lithiumation polyacetylene 35% and metal mixed powder 16%, wherein gold The weight ratio for belonging to metallic lithium powder in mixed-powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder and metallic titanium powder is 95:2:1.5: The nm-class silicon carbide material preparation method of 0.8:0.7, the high metal content are same as above.

Example IV

Amorphism silicon powder 2%, polysiloxanes 45%, lithiumation polyacetylene 30% and metal mixed powder 23%, wherein gold The weight ratio for belonging to metallic lithium powder in mixed-powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder and metallic titanium powder is 98:1:0.5: The nm-class silicon carbide material preparation method of 0.3:0.2, the high metal content are same as above.

Chemical analysis is carried out to the nanometer silicon carbide of prepared high metal content, the results showed that its ingredient contains following Elements Si, C, Li, Mg, Be, Al and Ti.When other experiment conditions are identical, only change the weight ratio of reactant each component, it is raw At high metal content nanometer silicon carbide structural chemical formula it is as shown in table 1, it can also be seen that metal elemental lithium from table 1 Ratio be apparently higher than the ratios of other metallic elements.

Table 1 is the knot of the nanometer silicon carbide for the high metal content that different component combination is prepared under lasing condition the same terms Structure chemical formula

Electrochemical property test is carried out to the nm-class silicon carbide material of high metal content prepared by embodiment one.

Fig. 1 is the scanning electron microscope image of the nanometer silicon carbide of prepared high metal content, the results showed that the crystal of product Pattern is mainly nano wire boundling, is about 1 with a small amount of sheet and micro irregular spherulite, the diameter of the nano wire ~40nm, length are about 10um.Direction of growth collection is bundled together along the line.Fig. 2 is the nano silicon carbide of prepared high metal content The X-ray diffractogram of silicon, the results showed that only there are two the characteristic peaks of silicon carbide, and the bright and sharp bottom of diffraction maximum profile is wide slow clear, and two The corresponding peak value in one, the angle a 2 θ is 35.2 °, peak intensity 20, and it is 60.2 ° that another, which corresponds to peak value, and peak intensity 100 shows institute The nanometer silicon carbide of the high metal content of preparation is cubic lattice silicon carbide, i.e. β-SiC.The other feature for having lacked silicon carbide spreads out Peak is penetrated, it is the diffraction information of non-crystalline state carborundum that explanation, which is quasi-crystalline state nanometer silicon carbide, and the diffraction peaks broadening protuberance in figure; The characteristics of these diffraction maximums, shows that this Process Production object is nanometer silicon carbide crystalline state, quasi-crystalline state and amorphous mixture phase.Such as Shown in Fig. 8, the nanometer silicon carbide cell configuration of high metal content, wherein black ball is silicon atom, and white is carbon atom or metal Atom, metallic atom replace the carbon atom lattice point of a quarter, form the nanometer silicon carbide of high metal content.

Two curves in Fig. 2 are that No. 1 and No. 25 x-ray in 30 wafer samples prepared in embodiment one is spread out Curve is penetrated, it can be seen from the figure that having no other peaks in curve, is shown in preparation process without other solid phases (such as metal single phase, stone Ink, carbon simple substance or other compound phases) it generates, it is the nanometer silicon carbide of pure high metal content.In addition, what is occurred in figure spreads out Two characteristic peaks that peak value is nanometer silicon carbide object phase x-ray diffraction are penetrated, these lack complete carborundum crystals diffraction maximum and show There are crystalline state nanometer carborundum crystal, nanometer amorphous carborundum crystals and nanometer quasi-crystalline state carborundum crystals in object phase constituent.According to It is calculated according to experimental result, synthetic ratio reaches 97%, and synthetic ratio described herein is exactly the weight percent with product and reactant It calculates.Illustrate that method of the present invention, prepared product purity are high.

The nanometer silicon carbide of high metal content prepared by embodiment two, three and four is tested for the property, as a result with Result in embodiment one is consistent: crystal morphology is nano wire collection pencil, with a small amount of sheet and micro irregular globular crystal Body;Structure cell is cubic lattice, i.e. β-SiC;Without other solid phases (such as metal single phase, graphite, carbon simple substance or otherization in preparation process Close object phase) it generates, it is the nanometer silicon carbide of pure high metal content;There is crystalline state nanometer carborundum crystal in object phase constituent, receive Rice amorphous state carborundum crystals and nanometer quasi-crystalline state carborundum crystals.

A kind of electrode slice of the nm-class silicon carbide material comprising above-mentioned high metal content, the electrode slice can be used as battery just Pole, preparation method are as follows: by weight, the nanometer silicon carbide of high metal content: carbon black: Kynoar (Pvdf)=85%: 8%:7% weighs the nanometer silicon carbide of 30g high metal content and the carbon black and Pvdf of corresponding weight, wherein carbon black is used as and leads Electric agent, Pvdf is as bonding agent.Three of the above substance is dissolved in N-Methyl pyrrolidone (NMP), for 24 hours after, even application In aluminium foil surface, i.e. collector is aluminium foil, forms 5um film, dries for 24 hours in 120~200 DEG C of vacuum oven.It takes out 12MPa pressure press mold is used on tablet press machine afterwards, is cut into the disk of diameter 1.5cm, producing quantity is 300.

20 are taken out, 20 button batteries, this kind are formed to electrode lithium piece, electrolyte and diaphragm with as cathode Battery is a kind of half-cell.Charge and discharge are carried out to the half-cell, setting charge and discharge window voltage is 4.2~0V, and current density is 0.2mA/cm2.Fig. 3 is cycle period-specific capacity-of 1~50 charge and discharge of positive plate-lithium half-cell prepared by the present invention Coulombic efficiency figure, Fig. 4 are 1~50 specific capacity of positive plate-lithium half-cell-voltage cycle test chart prepared by the present invention, Loop test the result shows that: first time discharge capacity reaches 890mAh/g.Charging capacity reaches 885mAh/g.Coulombic efficiency is 99.4%;Second of discharge capacity is 920mAh/g, charging capacity 910mAh/g.Coulombic efficiency is up to 98.9%;Third time is followed Ring, discharge capacity 890mAh/g, charging capacity 900mAh/g, coulombic efficiency reach 101.2%;10th cycle charging capacity 2500mAh/g, discharge capacity 2500mAh/g, coulombic efficiency 100%;50th circulation is such as the 10th circulation.This material The energy density of material reaches 2000Wh/kg, and average discharge volt platform has suffered 90% in 2.8V, in the range set of 3.8~2.0V Specific capacity.Energy density reaches 2000-1500Wh/kg.And its charging voltage flat roof area 0.01-0.08V has concentrated specific volume The 90% of amount.This half-cell cycle life reaches 20000 times.

The negative electrode tab of the nanometer silicon carbide active material containing this kind of high metal content is prepared, which can be used as battery Cathode, method particularly includes: by weight nanometer silicon carbide: carbon black: Kynoar (Pvdf)=85%:8%:7% weighs Three kinds of substances are dissolved in NMP by the carbon black and Pvdf of 50g nanometer silicon carbide and corresponding weight, for 24 hours after.Even application is in copper Foil surface, i.e. collector are copper foil, form 5um film, dry for 24 hours in 120~200 DEG C of vacuum oven.After taking-up 12MPa pressure press mold is used on tablet press machine, is cut into the disk of diameter 1.5cm, and producing quantity is 500.

50 are taken out, 50 button batteries, this kind are formed to electrode lithium piece, electrolyte and diaphragm with as cathode Battery is also a kind of half-cell.Charge and discharge are carried out to the half-cell, setting charge and discharge window voltage is 3.5~0V, current density For 0.2mA/cm2.Loop test the result shows that, first time discharge capacity reaches 1200mAh/g.Charging capacity reaches 1190mAh/ g.Coulombic efficiency is 99.2%.Second of discharge capacity is 2450mAh/g, charging capacity 2440mAh/g.Coulombic efficiency reaches 99.6%.Third time recycles, and discharge capacity 2450mAh/g, charging capacity 2450mAh/g, coulombic efficiency reach 100%.The 10 cycle charging capacity 2500mAh/g, discharge capacity 2500mAh/g, coulombic efficiency 100%.50th time circulation with the 10th time As circulation.The average discharge volt platform of this nanometer silicon carbide negative electrode active material in 3.50~0.01V, 4.1~ 3.5V range occupies 85% of specific capacity or more.Its charging voltage flat roof area 0.01-0.03V has concentrated the 90% of specific capacity. The half-cell cycle life that this nanometer silicon carbide and lithium are formed reaches 20000 times.

Above-mentioned conductive agent can be with are as follows: other carbonaceous materials: such as acetylene black, artificial graphite, graphite particle, natural stone Ink, carbon fiber or carbon nanotube;The metal powder or metallic fiber or metal tube of copper, nickel, aluminium, silver etc.;Or conducting polymer, Such as polyphenylene derivatives.However, conductive agent is without being limited thereto, conductive agent can be a variety of materials for being used as conductive agent in the art In any one.Above-mentioned adhesive can also be polyacrylonitrile, vinylidene fluoride/hexafluoropropylene copolymer, poly- methyl-prop E pioic acid methyl ester or polytetrafluoroethylene (PTFE).Solvent can also be acetone, water.Adhesive and solvent are not limited to these materials, can be this Any one in a variety of materials used in field.

Electrode material, conductive agent, adhesive and solvent amount can be in identical water with the conventional amount used in lithium battery It is flat.

The shape and size of the electrode slice can also be changed according to actual needs, and the application is using diameter The disk of 1.5cm.

A kind of full silicon carbide lithium secondary battery, electrode used therein include the nm-class silicon carbide material of above-mentioned high metal content. Full silicon carbide lithium secondary battery of the present invention refers to, anode is done with above-mentioned positive plate (its collector is aluminium foil), with above-mentioned Negative electrode tab (its collector is copper foil) does the lithium secondary battery that cathode is constituted.The preparation side of this kind of full silicon carbide lithium secondary battery Method are as follows: after vacuumizing vacuum glove box, be passed through inert gas, make to reach 1 atmospheric pressure in vacuum glove box, (1) takes 100 Above-mentioned positive plate, by it with to electrode lithium piece, electrolyte and celguard diaphragm, sequence is packed into dismountable superhard plastics electricity A kind of half-cell is formed in the shell of pond.After shelving 48h, in 0.2mA/cm2It discharges under current density, until positive plate specific capacity Reach 2450mAh/g.(2) dismantling above-mentioned superhard plastic battery shell in an inert atmosphere (can be cylinder, rectangle, film Type etc.), the positive plate for being full of lithium ion is taken out, and fast transfer adds celguard diaphragm into CR2025 type stainless steel case, folded In addition stating negative electrode tab, electrolyte is injected, encapsulation forms full silicon carbide lithium secondary battery together.Electrolyte used preferably contains carbon Vinyl acetate, propene carbonate, methyl propyl carbonate, dipropyl carbonate, LiPF61M electrolyte;And ethylene carbonate may be selected Ester: propene carbonate: methyl propyl carbonate: dipropyl carbonate: LiPF6Proportion be 2:2:2:1:1.

By the full silicon carbide lithium secondary battery at change 72h after, in voltage window 4.2V~0.01V, current density 0.2mA/cm2Lower progress charge discharge circulation, electrochemical cell circulation dynamics test result are as shown in table 2.By table 2 As it can be seen that the electro-chemical test that example cycle characteristics tests full silicon carbide battery sample show first time cycle capacity loss between Within 0.09%.Specific capacity reaches near 2450mAh/g at most of battery the 30th time, and coulombic efficiency is close to 100%, this Battery has height ratio capacity, the excellent properties of long-life.

Fig. 5 be full silicon carbide lithium secondary battery the 1st~8000 voltage-capacity figure, charging/discharging voltage window be 4.2~ 0.3V, charging and discharging currents 0.2mA/cm2;It can be seen that first time coulombic efficiency is 99.9%, the 8000th charge and discharge library For human relations efficiency still near 99.99%, discharge platform occupies 80% or more of total specific capacity in 4.0~3.2V range;Fig. 6 For the 1st~50 voltage-capacity figure of the full silicon carbide lithium secondary battery of selected another set sample, charging/discharging voltage window is 4.2~0.3V, charging and discharging currents 0.2mA/cm2;As can be seen from the figure: this full silicon carbide lithium secondary battery discharge platform In 3.5V;Fig. 7 is full silicon carbide lithium secondary battery energy density-cycle diagram, discharge energy density reaches 1600~ 2000Wh/kg range, power density reach 1800~2000W/kg.Its cycle period reaches 20000, and energy density and power are close Degree constantly increases with cycle period, forms platform after being maintained at a high extreme value.This kind of full silicon carbide lithium secondary battery has The advantages of service life is long, capacity is high, good cycle.

The circulation dynamics test result of the full silicon carbide lithium secondary battery of table 2

Above-described embodiment elaborates the present invention.Certainly, above description is not limitation of the present invention, the present invention Be also not limited to above-mentioned example, related technical personnel within the essential scope of the present invention made variation, retrofit, add and add deduct Less, it replaces, also belongs to protection scope of the present invention.

Claims (10)

1. a kind of preparation method of the nm-class silicon carbide material of high metal content, which comprises the following steps:
It (1) is reaction starting material, the gold with amorphism silicon powder, polysiloxanes, lithiumation polyacetylene and metal mixed powder Belong to mixed-powder to be mixed by metallic lithium powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder, metallic titanium powder;
(2) prepared reaction starting material is uniformly mixed, then dries, is finally pressed into disk;
(3) multiple medium blocking discharge electrodes are set in reaction vacuum chamber, and the disk is put in dielectric barrier discharge electricity Between pole, multi rack laser is uniformly arranged outside reaction vacuum chamber;
(4) vacuum chamber will be reacted, will be powered, dielectric barrier discharge generates plasma, laser transmitting laser vaporization circle Piece stands 72h.
2. a kind of preparation method of the nm-class silicon carbide material of high metal content according to claim 1, which is characterized in that The weight ratio of the amorphism silicon powder, polysiloxanes, lithiumation polyacetylene and metal mixed powder are as follows: 0.1~2%:45~ 54.5%:30~45%:0.4~23%;The metallic lithium powder, metallic aluminium powder, metallic beryllium powder, metal magnesium powder and metallic titanium powder Weight ratio is 90~99%:0.5~3%:0.1~3%:0.2~2%:0.2~2%.
3. a kind of preparation method of the nm-class silicon carbide material of high metal content according to claim 2, which is characterized in that The disk is placed in the dish type graphite boat on reaction chamber central turnplate deck in step (3), in reaction chamber inscribed circle Medium blocking discharge electrode is arranged in the both ends of at least one diameter, and the disk is located among two medium blocking discharge electrodes;Institute Stating medium blocking discharge electrode is high-frequency and high-voltage electrode, and is curved surface tiles, and curvature is consistent with the curvature of reaction chamber wall.
4. a kind of preparation method of the nm-class silicon carbide material of high metal content according to claim 3, which is characterized in that The medium blocking discharge electrode and example boat are in same level, and the medium blocking discharge electrode is multilayered structure, lean on One layer of nearly disk is tungsten metal mesh, and one layer close to reaction chamber wall is metal electrode, between tungsten metal mesh and metal electrode To gather inclined tetrafluoroethene, the metal electrode, gather inclined tetrafluoroethene, tungsten metal mesh with a thickness of 1~3cm, between both adjacent It is divided into 1~5cm.
5. a kind of preparation method of the nm-class silicon carbide material of high metal content according to claim 2, which is characterized in that The laser is all solid state ti sapphire laser, and the wavelength of transmitting laser is 460nm and 540nm, and laser gun axis line passes through Deck center, and 30 ° of angles are formed with deck surface.
6. a kind of preparation method of the nm-class silicon carbide material of high metal content according to claim 5, which is characterized in that Before step (4) vacuumizes, one piece of clean stainless steel plate is set for collecting product in a vacuum chamber, then takes out reaction chamber Vacuum reaches 1mTorr;The power supply of medium blocking discharge electrode is opened, discharges and generates plasma, after 5min, opens laser Power supply emits ultrashort pulse, disk vaporization.
7. a kind of electrode, which is characterized in that the nano silicon carbide comprising high metal content according to any one of claims 1 to 6 The nanometer silicon carbide active material of high metal content prepared by the preparation method of silicon materials.
8. a kind of full silicon carbide lithium secondary battery, which is characterized in that the anode and cathode of the battery are as claimed in claim 7 Electrode, and anode is different with the collector of cathode;The anode and cathode are separated by Celgard polymer film, and inject electricity Solve liquid.
9. a kind of full silicon carbide lithium secondary battery according to claim 8, which is characterized in that the electrolyte be include carbon Vinyl acetate, propene carbonate, methyl propyl carbonate, dipropyl carbonate, LiPF6 1M electrolyte;Select ethylene carbonate: carbonic acid Acrylic ester: methyl propyl carbonate: dipropyl carbonate: LiPF6 Proportion be 2:2:2:1:1.
10. a kind of full silicon carbide lithium secondary battery according to claim 8 or claim 9, which is characterized in that the library for the first time of the battery Human relations efficiency reaches 99.9%, and discharge platform is 4.1~3.5V, and specific capacity reaches 2450mAh/g, and discharge energy density reaches 1600 ~2000Wh/kg, power density reach 1800~2000W/kg, and cycle period can achieve 20000 times.
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