CN105428618A - Preparation method for shell-core type carbon-coated metal sulfide nano-composite particles and application of particles - Google Patents

Preparation method for shell-core type carbon-coated metal sulfide nano-composite particles and application of particles Download PDF

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CN105428618A
CN105428618A CN201510796864.3A CN201510796864A CN105428618A CN 105428618 A CN105428618 A CN 105428618A CN 201510796864 A CN201510796864 A CN 201510796864A CN 105428618 A CN105428618 A CN 105428618A
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carbon
powder
sulfide nano
nano
inert gas
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CN105428618B (en
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黄昊
高嵩
余洁意
董星龙
吴爱民
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Dalian University of Technology
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Dalian University of Technology
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a preparation method for shell-core type carbon-coated metal sulfide nano-composite particles. The obtained composite particles as a lithium ion battery negative electrode material are applied to the field of lithium ion batteries. The method comprises the steps: adding a certain proportion of carbon source-containing substances and inert gases into an automatic control direct-current arc metal nano-powder production device, and evaporating a metal raw material to obtain a carbon-coated metal nanoparticle precursor; and then mixing the precursor with sulfur powder, putting a mixture into a high-pressure sealed reaction kettle to perform heat treatment to obtain carbon-coated metal sulfide nano-composite particles, and making a lithium ion electrode plate by taking a carbon-coated iron sulfide nano-composite material as an active substance. The method has the advantages that low-temperature sulfuration is performed by taking in-situ synthesized carbon-coated iron and tin nanoparticles as precursors to obtain carbon-coated iron sulfide and tin sulfide nano-composite particles; the lithium insertion/extraction capacity density and the cycle stability are relatively high; the raw material cost is low; a process is simple; the large-scale preparation can be realized; and the industrial production requirements are met.

Description

A kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle and application thereof
Technical field
The invention belongs to nano material preparation technology and application, relate to a kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle, nano-complex particle is applied in field of lithium ion battery as lithium ion battery negative material.
Background technology
Lithium ion battery (also referred to as lithium rechargeable battery or lithium-ions battery) has the advantages such as quality is light, energy density is large, voltage is high, volume is little, good cycle, memory-less effect, be considered to 21 century one of energy having application prospect most, and be widely used in traffic, communication and regenerative resource department.At present because graphite has length circulation timei, the in a large number advantage such as existence and low cost to be widely used the negative material as commercial Li-ion battery, although material with carbon element has good cycle performance in as lithium ion battery negative material, but its low theoretical capacity (372mAh/g), can not meet the demand that society is growing to the energy.Therefore, find and develop that a kind of energy density is high, with low cost, the material of the lithium ion battery negative material of high charge-discharge speed and high cyclical stability carrys out the study hotspot that alternative graphite has become current.
In recent years along with the further investigation to lithium ion battery negative material, in succession there is different types of negative material with storage lithium performance, the such as compound system etc. of metal simple-substance nano particle, alloy nano particle, metal sulfide, metal nitride, transition metal oxide, metal phosphide and these materials.Wherein, metal sulfide material is owing to having the low and advantages of environment protection of higher specific capacity, energy density, cost and being paid close attention to widely.As metal sulfide (MS x(M:Mn, Fe, Co, Ni, Cu etc.)) series material, the people such as Y.Yang report the coated FeS of employing two one-step hydrothermal synthesis carbon in [JournalofPowerSources (2015 (274) 685-692)] 2composite material, it can be used as lithium ion cell electrode negative material, in discharge process first, obtains and FeS 2the specific capacity 830mAh/g that theoretical capacity (890mAh/g) is close, but after it is circulated to 50 times, its specific capacity is only 110mAh/g.In order to improve FeS further 2as specific capacity and the energy density of negative material, some new coated FeS of synthesis carbon 2composite material and preparation method thereof needs research further.
The research of metal sulfide mainly comes from lithium ion and is combined with sulphur and forms lithium intercalation compound Li 2s, these sulfide itself have comparatively height ratio capacity, but need to carry out compound with carbon to improve the conduction of charge carrier in charge and discharge process.Patent [CN104835961A] discloses a kind of lithium ion battery negative material, i.e. the preparation method of material with carbon-coated surface transient metal sulfide.The method adopts hydro thermal method, is dispersed in by transient metal sulfide in D/W, obtains the coated transient metal sulfide of carbon after hydro-thermal and high-temperature burning process.The coated transient metal sulfide electrode of the carbon that the method obtains first capacitance is only 380mAh/g, and method used in preparation process is more consuming time, is not suitable for suitability for industrialized production.Patent [CN104716319A] discloses the preparation method of a kind of carbon-clad metal sulfide multipole material as sodium ion secondary battery negative material.The method is by the mixed solution of water-soluble for one or more slaines (ammonium heptamolybdate and ferric nitrate etc.) and ethanol; reactor is put into after adding the salt of inertia nano wire template and sulfur-bearing or sulphur; through heating, cooling, centrifugal, washing, after drying; the carbon composite metal sulfide material that obtains of heat treatment under nitrogen protection; though the material that the method obtains has higher stable circulation performance; but material manufacturing cycle is longer; consume energy larger; preparation technology is more complicated, still needs to do further improvement.
Usually for simple FeS 2material, although have very high lithium storage content, as negative active core-shell material, in lithium ion battery charge and discharge cycles process, the deintercalation repeatedly of lithium easily makes electrode volumetric expansion efflorescence inefficacy gradually, and the chemical property of electrode is deteriorated, and capacity reduces.And material with carbon element has very high hardness and intensity, the coated FeS of structure carbon 2nano-powder, effectively can suppress volumetric expansion, improves material circulation performance.Therefore present invention incorporates the cyclical stability of material with carbon element and the height ratio capacity of iron sulfide, synthesis core-shell type carbon-clad metal sulfide nano composite material, is conducive to the application at lithium ion battery negative material.
Automatic control direct-current arc metal nano powder production equipment (ZL200410021190.1) generates room, powder granularity grading room, powder dust trapping chamber, powder handling room, vacuum system, gas-circulating system, Hydraulic Power Transmission System, water-cooling system and programming Control system by powder and forms; Powder generates in room and installs negative electrode and anode, and is connected with external hydraulic transmission and programming Control system through powder generation locular wall; When preparing powder, material is loaded anode, form the gap of 10 ~ 30mm with negative electrode, whole equipment vacuumizes, logical cooling water.After passing into active gases and condensed gas, start power supply and starting the arc device, form electric arc between a cathode and an anode, material starts evaporating cold coalescence and forms nano-powder particle.
Utilize and automatically control that direct-current arc metal nano powder production equipment is prepared Carbon en capsulated nanomaterials and had that technique is simple, preparation in macroscopic quantity and be beneficial to the advantages such as suitability for industrialized production.The excellent properties such as height ratio capacity, high cycle life can be obtained as electrode of lithium cell negative material using the nano-powder of preparation.
Summary of the invention
Not enough and the Improvement requirement for prior art, the invention provides a kind of preparation method and technique of core-shell type carbon-clad metal sulfide nano-complex particle, using the carbon-clad metal nano particle of fabricated in situ as presoma, carbon-clad metal sulfide nano-complex particle is obtained through cryogenic vulcanization technique, this nano-complex particle has shell-caryogram nanostructure that graphitized carbon ball is shell, metal sulfide is core, improves embedding/de-lithium capacity and cyclical stability: namely effectively raise specific capacity under high rate charge-discharge condition; Under the protection of graphitized carbon shell, electrode material structure is effectively safeguarded, improves the stable circulation performance of electrode; 760mAh/g reversible capacity can be obtained in lithium ion battery with nonaqueous electrolyte.
In order to achieve the above object, the equipment that the present invention adopts is automatically control direct-current arc metal nano powder production equipment, and technical scheme is:
Automatically the anode of powder generation room controlling direct-current arc metal nano powder production equipment puts into block or powder raw metal, and adds carbon source and inert gas, evaporated metal raw material, obtain carbon-clad metal nano particle presoma.Then put into high pressure sealing reactor after being mixed under anhydrous and oxygen-free condition with sulphur powder by carbon-clad metal nano particle presoma to heat-treat, obtain carbon-clad metal sulfide nano composite material, specifically comprise the following steps:
(1) in the powder generation room automatically controlling direct-current arc metal nano powder production equipment, add 20 ~ 80g raw metal, carbon source and inert gas, evaporated metal raw material obtains carbon covered metal nanoparticle precursor;
Described raw metal is positioned over powder and generates on the anode of room, and raw metal is one or more combinations in iron, manganese, cobalt, nickel, copper, zinc, tin, adopts block or powder;
When described carbon source is gaseous state, carbon source is one or more mixing in methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene, and the ratio of carbon source and inert gas is 1:5 ~ 4:1;
When described carbon source is liquid, in carbon source and raw metal placing graphite crucible, graphite crucible being placed on powder generates on the anode of room, carbon source is one in ethanol, methyl alcohol or propyl alcohol and combination thereof, generates in room often add the inert gas that 5 ~ 50ml carbon source passes into 0.01 ~ 0.03MPa at powder;
When described carbon source is solid-state, be placed on the anode of powder generation room after carbon source and raw metal mixing briquetting, carbon source and raw metal mass ratio are 1:3 ~ 5:1; Carbon source is carbon and allotrope thereof, the one in glucose or polypyrrole (PPy) and combination thereof, and adding inert gas volume is 0.01MPa ~ 0.06MPa;
Described inert gas is one and the combination thereof of argon gas, helium or neon;
(2) mix under the anhydrous condition of carbon covered metal nanoparticle precursor anaerobic with sulphur powder, put into high pressure sealing reactor, under inert gas shielding, be warming up to 200 ~ 500 DEG C after solid phase reaction 1 ~ 3h, be cooled to room temperature, obtain carbon-clad metal sulfide nano-complex particle;
The condition of described anhydrous and oxygen-free is that water content is less than 1/10000000th, and oxygen content is less than 1/10000000th;
The mass ratio of described presoma and sulphur powder is 1:1 ~ 1:3;
Described inert gas shielding is that to put into inert gas volume be 0.01MPa ~ 0.08MPa;
Described inert gas is one and the combination thereof of argon gas, helium, neon or nitrogen;
The nano metal sulfide compound particle of above-mentioned preparation is for the preparation of lithium-ion electric pole piece, amount of conductive agent and appropriate binding agent is added in carbon-clad metal sulfide nano-complex particle, be dispersed in solvent and obtained electrode material, described electrode material is applied to the single or double of conduction current collector, under vacuum heating conditions by removal of solvents after, prepare the electrode slice of different size according to battery specifications.
Described carbon-clad metal sulfide nano-complex particle and the mass percent of binding agent are 50 ~ 90:10; The mass percent of conductive agent is less than 40;
Described conductive agent is carbon black conductive agent (acetylene black, SuperP, SuperS, 350G, carbon fiber (VGCF), carbon nano-tube (CNTs), Ketjen black (KetjenblackEC300J, KetjenblackEC300JD)) etc.), one in graphite agent (KS-6, SFG-6 etc.) or Graphene and combination thereof;
Described binding agent is one and the combination thereof of polyvinylidene chloride (PVDF), polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) or polyvinyl alcohol (PVA);
Described solvent is 1-METHYLPYRROLIDONE (NMP), dinethylformamide (DMF) or deionized water;
Described conduction current collector is iron foil, nickel foil, aluminium foil, Copper Foil, foam copper, nickel foam, foamed aluminium or foamed iron.
Beneficial effect of the present invention is:
(1) preparation process is simple, and low raw-material cost, does not produce harmful substance, can suitability for industrialized production;
(2) prepare in carbon-clad metal sulfide nano-complex particle process, the existence of carbon shell can suppress the oxidation of metallic element, effectively prevents the reunion of nano particle in heat treatment process;
(3) in heat treatment process, carbon shell provides sulphur atom to enter diffusion admittance in core, sulphur atom and core metal is reacted and generates metal sulfide, the core-shell type nano structure that finally to be formed with carbon be shell, metal sulfide is core;
(4) existence of graphitized carbon shell provides lithium ion exchanged passage, and carbon shell has very high intensity, effectively suppresses the volumetric expansion of metal sulfide, the efflorescence avoiding metallic sulfide nano-particle to cause because of embedding/de-lithium process and inefficacy;
(5) sulfide itself has height ratio capacity, is combined defines high lithium intercalation compound Li with lithium 2s, graphitized carbon shell material provides more avtive spot to be combined with lithium ion, forms LiC 6phase also has good circulation characteristic.Based on the advantage of two kinds of materials, synthesized nano material has the comprehensive advantage such as height ratio capacity and high cyclical stability.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the coated iron sulfide nano-complex particle of carbon that embodiment 1 is synthesized.
Fig. 2 is the Raman spectrum (Raman) of the coated iron sulfide nano-complex particle of carbon that embodiment 1 is synthesized.
Fig. 3 is the charging and discharging curve of the coated iron sulfide nano-complex particle of carbon under the current density of 500mA/g that embodiment 1 is synthesized.
Fig. 4 is the stable circulation linearity curve of the coated artificial gold nano-complex particle of carbon under the current density of 500mA/g that embodiment 1 is synthesized.
Fig. 5 is X-ray diffraction (XRD) collection of illustrative plates of the coated artificial gold nano-complex particle of carbon of the 2-in-1 one-tenth of embodiment.
Fig. 6 is the Raman spectrum (Raman) of the coated artificial gold nano-complex particle of carbon of the 2-in-1 one-tenth of embodiment.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Embodiment one:
Get about 40g iron block to put into the powder automatically controlling direct-current arc metal nano powder production equipment and generate on the anode of room and evaporate, pass into methane and argon gas that ratio is 3:4 simultaneously, obtain carbon-encapsulated iron nanoparticles presoma; Put in high pressure sealing reactor after this presoma is mixed with sulphur powder by 2:3 mass ratio in glove box (ensureing anhydrous and oxygen-free environment); reactor is heated to 400 DEG C and heat-treats 1.5h under 0.05MPa argon shield; be cooled to room temperature, obtain the coated iron sulfide nano composite material of carbon.
Above-mentioned carbon-clad metal sulfide nano composite material is made into lithium-ion electric pole piece.Wherein electrode slice in mass ratio 80% the coated iron sulfide nano composite material of carbon, the Ketjen black of 10% and polyvinylidene fluoride (PVDF) binding agent of 10% mix, add appropriate 1-METHYLPYRROLIDONE (NMP) to dissolve, slurry is coated in obtained electrode on copper current collector; This experimental electrode is 100 DEG C of dry 12h in vacuum drying oven, in high-purity argon gas atmosphere glove box, assemble battery.Wherein electrolyte is the LiPF of 1mol/L 6solution, solvent is volume ratio 1:1 ethylene carbonate (EC) and diethyl carbonate (DC).Taking polypropylene as barrier film, is that lithium sheet is assembled into CR2025 button cell to electrode.
The present invention obtains the lithium ion battery negative electrode using the coated iron sulfide nano composite material of carbon as active material, at room temperature, within the scope of 0.01 ~ 3V, with 500mA/g current density, charge and discharge test is carried out to battery, obtain the specific capacity of 760mAh/g, stable cycle performance.
The XRD figure of the coated iron sulfide nano composite material of the carbon that embodiment one obtains as shown in Figure 1.Determine in this composite material main containing iron sulfide and a small amount of unvulcanized fe phase by diffraction maximum in figure.
The Raman spectrum (Raman) of the coated iron sulfide nano composite material of the carbon that embodiment one obtains as shown in Figure 2.Can determine that carbon coated in this material is containing a large amount of defect by the relative intensity at D peak and G peak in figure.
In embodiment one, Fig. 3 and Fig. 4 is respectively under room temperature within the scope of 0.01 ~ 3V, the charging and discharging curve carried out with the current density of 500mA/g and stable circulation performance curve.As seen from the figure, when the coated iron sulfide composite material of the carbon that the present invention obtains is as lithium ion battery negative material, have the reversible specific capacity first close to 870mAh/g, it is highly stable that Fig. 4 shows its cycle performance.After the 50th circulation, its reversible specific capacity still remains on 760mAh/g.
Embodiment two:
After getting about 20g iron powder and 15g carbon dust Homogeneous phase mixing, be pressed into block and put into and automatically control anode that direct-current arc metal nano powder production equipment powder generates room evaporates, pass into 0.06MPa helium simultaneously, obtain carbon-encapsulated iron nanoparticles presoma; Put in sealed reactor after being mixed with sulphur powder by 1:3 mass ratio in glove box by this presoma, reactor is heated to 500 DEG C and heat-treats 1h under 0.01MPa nitrogen protection, is cooled to room temperature, obtains the coated iron sulfide nano composite material of carbon.
Embodiment three:
Getting about 80g iron powder puts into graphite crucible, add 20 ~ 40ml ethanol, graphite crucible is put on the automatic anode controlling the powder generation room of direct-current arc metal nano powder production equipment and evaporate, pass into 0.01MPa neon simultaneously and obtain carbon-encapsulated iron nanoparticles presoma; Put after being mixed with sulphur powder by 1:1 mass ratio in glove box by this presoma in high pressure sealing reactor, reactor is heated to 250 DEG C and heat-treats 3h under the protection of 0.08MPa helium, is cooled to room temperature, obtains the coated iron sulfide nano composite material of carbon.
Embodiment four:
Get about 20g block tin body to put into and automatically control anode that direct-current arc metal nano powder production equipment powder generates room evaporates, pass into methane and argon gas that ratio is 4:1 simultaneously, obtain carbon covered stannum rice compound particle presoma; Put after this presoma is mixed with sulphur powder by 1:2 mass ratio in glove box in high pressure sealing reactor; reactor is heated to 450 DEG C and heat-treats 1.5h under 0.02MPa nitrogen protection; be cooled to room temperature, obtain the coated artificial gold nano composite material of carbon.
The XRD figure of the coated artificial gold nano composite material of the carbon that embodiment four obtains as shown in Figure 5.Determine in this composite material main containing artificial gold and a small amount of unvulcanized simple substance tin phase by diffraction maximum in figure.
The Raman spectrum (Raman) of the coated artificial gold nano composite material of the carbon that embodiment four obtains as shown in Figure 6.Can determine that carbon coated in this material is containing a large amount of defect by the relative intensity at D peak and G peak in figure.

Claims (6)

1. a preparation method for core-shell type carbon-clad metal sulfide nano-complex particle, is characterized in that, comprise the following steps:
The first step, generate in room at the powder automatically controlling direct-current arc metal nano powder production equipment and add raw metal, carbon source and inert gas, evaporated metal raw material obtains carbon covered metal nanoparticle precursor;
Described raw metal is 20 ~ 80g, is placed on powder and generates on the anode of room;
When described carbon source is gaseous state, the ratio of carbon source and inert gas is 1:5 ~ 4:1;
When described carbon source is liquid, in carbon source and raw metal placing graphite crucible, graphite crucible is placed on powder and generates on the anode of room, generates in room often add the inert gas that 5 ~ 50ml carbon source passes into 0.01 ~ 0.03MPa at powder;
When described carbon source is solid-state, be placed on the anode of powder generation room after carbon source and raw metal mixing briquetting, carbon source and metal-powder mass ratio are 1:3 ~ 5:1, and adding inert gas volume is 0.01MPa ~ 0.06MPa;
Second step, carbon covered metal nanoparticle precursor is mixed with sulphur powder under anhydrous and oxygen-free condition and puts into high pressure sealing reactor, under inert gas shielding, after 200 ~ 500 DEG C of conditioned response 1 ~ 3h, be cooled to room temperature, obtain carbon-clad metal sulfide nano-complex particle;
Described anhydrous and oxygen-free is that water content is less than 1/10000000th, and oxygen content is less than 1/10000000th;
Described carbon covered metal nanoparticle precursor and the mass ratio of sulphur powder are 1:1 ~ 1:3.
2. the preparation method of a kind of core-shell type carbon-clad metal sulfide nano-complex particle as claimed in claim 1, it is characterized in that, described raw metal is one or more combinations in iron, manganese, cobalt, nickel, copper, zinc, tin, adopts block or powder.
3. the preparation method of a kind of core-shell type carbon-clad metal sulfide nano-complex particle as claimed in claim 1 or 2, it is characterized in that, described gaseous carbon source is one or more mixing in methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene; Described liquid carbon source is one and the combination thereof of ethanol, methyl alcohol or propyl alcohol; Described solid-state carbon source is carbon and allotrope thereof, the one in glucose or polypyrrole PPy and combination thereof.
4. the preparation method of a kind of core-shell type carbon-clad metal sulfide nano-complex particle as claimed in claim 1 or 2, it is characterized in that, the inert gas described in the first step is one and the combination thereof of argon gas, helium or neon; Inert gas described in second step is one and the combination thereof of argon gas, helium, neon or nitrogen, and the inert gas volume described in second step is 0.01MPa ~ 0.08MPa.
5. the preparation method of a kind of core-shell type carbon-clad metal sulfide nano-complex particle as claimed in claim 3, it is characterized in that, the inert gas described in the first step is one and the combination thereof of argon gas, helium or neon; Inert gas described in second step is one and the combination thereof of argon gas, helium, neon or nitrogen, and the inert gas volume described in second step is 0.01MPa ~ 0.08MPa.
6. the arbitrary described a kind of core-shell type carbon-clad metal sulfide nano-complex particle of claim 1-5 is for the preparation of lithium-ion electric pole piece, it is characterized in that, comprise the following steps: in carbon-clad metal sulfide nano-complex particle, add conductive agent and binding agent, be dispersed in solvent and obtain electrode material; Electrode material is applied to the single or double of conduction current collector, under vacuum heating conditions by removal of solvents after, prepare the electrode slice of different size according to battery specifications;
Described carbon-clad metal sulfide nano-complex particle and the mass percent of binding agent are 50 ~ 90:10, and the mass percent of conductive agent is less than 40;
Described conductive agent is carbon black conductive agent, the one of graphite agent or Graphene and combination thereof;
Described binding agent is one and the combination thereof of polyvinylidene chloride PVDF, polytetrafluoroethylene PTFE, sodium carboxymethylcellulose CMC, styrene butadiene rubber sbr or PVAC polyvinylalcohol;
Described solvent is 1-METHYLPYRROLIDONE NMP, dinethylformamide DMF or deionized water;
Described conduction current collector is iron foil, nickel foil, aluminium foil, Copper Foil, foam copper, nickel foam, foamed aluminium or foamed iron.
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CN115069177B (en) * 2022-06-16 2023-09-08 中国科学院福建物质结构研究所 Metal sulfide-carbon composite material with yolk-eggshell structure and preparation method and application thereof

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