CN105428618B - A kind of preparation method and applications of core-shell type carbon-clad metal sulfide nano-complex particle - Google Patents

A kind of preparation method and applications of core-shell type carbon-clad metal sulfide nano-complex particle Download PDF

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CN105428618B
CN105428618B CN201510796864.3A CN201510796864A CN105428618B CN 105428618 B CN105428618 B CN 105428618B CN 201510796864 A CN201510796864 A CN 201510796864A CN 105428618 B CN105428618 B CN 105428618B
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carbon source
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CN105428618A (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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    • 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 present invention provides a kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle, and nanometer is applied in field of lithium ion battery using gained compound particle as lithium ion battery negative material.The material and inert gas of a certain proportion of carbonaceous sources are added in direct-current arc metal nano powder production equipment is automatically controlled, evaporated metal raw material, obtains carbon-clad metal nano particle presoma；Then it is put into high pressure sealing reactor and is heat-treated after presoma is mixed with sulphur powder, obtain carbon-clad metal sulfide nano composite material, iron powder nano complex material is vulcanized as active material using carbon coating, makes lithium-ion electric pole piece.The advantage of the invention is that presoma is used as using the carbon-encapsulated iron of fabricated in situ, sijna rice corpuscles; cryogenic vulcanization obtains carbon coating iron sulfide, artificial gold nano-complex particle; with higher Li insertion extraction capacity density and cyclical stability; low raw-material cost; technique is simple; can prepare with scale, be adapted to industrialization production requirements.

Description

A kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle and its Using
Technical field
The invention belongs to nano material preparation technology and application field, is related to a kind of core-shell type carbon-clad metal sulfide and receives The preparation method of rice compound particle, nano-complex particle are 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) have light weight, energy density it is big, The advantages that voltage height, small volume, good cycle, memory-less effect, it is considered to be 21 century most have application prospect the energy it One, and be widely used in traffic, communication and regenerative resource department.At present because graphite has circulation time long, a large amount of In the presence of and it is inexpensive the advantages that be widely used negative material as commercial Li-ion battery, although carbon material is being made To have preferable cycle performance in negative electrode of lithium ion battery material, but its low theoretical capacity (372mAh/g), it can not meet The today's society demand growing to the energy.Therefore, find and develop that a kind of energy density is high, cost is cheap, high charge-discharge The material of the lithium ion battery negative material of speed and high circulation stability turns into current study hotspot to substitute graphite.
In recent years with the further investigation to lithium ion battery negative material, occur in succession different types of with storage lithium The negative material of performance, such as metal simple-substance nano-particle, alloy nano particle, metal sulfide, metal nitride, transition gold Belong to compound system of oxide, metal phosphide and these materials etc..Wherein, metal sulfide material is due to higher Specific capacity, energy density, cost be low and advantages of environment protection and widely paid close attention to.Such as metal sulfide (MSx(M:Mn, Fe, Co, Ni, Cu etc.)) series material, Y.Yang et al. is in [Journal of Power Sources (2015 (274) 685- 692) reported in] using two one-step hydrothermals synthesis carbon coating FeS2Composite, as lithium ion cell electrode negative pole Material, in discharge process first, acquisition and FeS2The close specific capacity 830mAh/g of theoretical capacity (890mAh/g), but After it is recycled to 50 times, its specific capacity is only 110mAh/g.In order to further improve FeS2As negative material specific capacity and Energy density, some new synthesis carbon coating FeS2Composite material and preparation method thereof need to be studied further.
The research of metal sulfide is mostly derived from lithium ion and combines to form lithium intercalation compound Li with sulphur2S, these sulfide sheets Body has high specific capacity, but needs in charge and discharge process to carry out compound improving the conduction of carrier with carbon.Patent [CN 104835961A] disclose the preparation method of lithium ion battery negative material, i.e. material with carbon-coated surface transient metal sulfide a kind of. This method uses hydro-thermal method, transient metal sulfide is dispersed in D/W, by hydro-thermal and high-temperature burning process After obtain carbon coating transient metal sulfide.Capacitance is only the carbon coating transient metal sulfide electrode that this method obtains first 380mAh/g, and method used in preparation process is relatively time-consuming, is not suitable for industrialized production.Patent [CN 104716319A] disclose a kind of preparation of carbon-clad metal sulfide multipole material as sodium ion secondary battery negative material Method.One or more metal salts (ammonium heptamolybdate and ferric nitrate etc.) are dissolved in the mixed solution of water and ethanol by this method, add It is put into reactor after entering the salt or sulphur of inertia nanometer line template and sulfur-bearing, by heating, cooling down, centrifuging, washing, dries Afterwards, the carbon composite metal sulfide material being thermally treated resulting under nitrogen protection, though the material that this method obtains is with higher Stable circulation performance, but material manufacturing cycle is longer, and power consumption is larger, and preparation technology is more complicated, still needs to do further improvement.
Generally for simple FeS2For material, although with very high lithium storage content, negative active core-shell material is used as, During lithium ion battery charge and discharge cycles, the deintercalation repeatedly of lithium easily makes electrode volume expand gradual efflorescence failure, makes electricity The chemical property of pole is deteriorated, and capacity reduces.And carbon material has very high hardness and intensity, construction carbon coating FeS2Nano powder It body, can effectively suppress volumetric expansion, improve material circulation performance.Therefore present invention incorporates the cyclical stability of carbon material and The height ratio capacity of iron sulfide, core-shell type carbon-clad metal sulfide nano composite material is synthesized, is advantageous to bear in lithium ion battery The application of pole material.
Automatically control direct-current arc metal nano powder production equipment (ZL200410021190.1) and room, powder are generated by powder Body grading room, powder dust trapping chamber, powder handling room, vacuum system, gas-circulating system, Hydraulic Power Transmission System, water cooling system System and programming Control system composition；Negative electrode and anode are installed in powder generation room, and locular wall and external hydraulic are generated through powder Transmission connects with programming Control system；When preparing powder, anode is charged material into, 10~30mm gap is formed with negative electrode, it is whole Individual equipment vacuumizes, and leads to cooling water.After being passed through active gases and condensed gas, startup power supply and starting the arc device, in negative electrode and anode Between form electric arc, material starts evaporative condenser and forms nano-powder particle.
Have technique simple using automatically controlling direct-current arc metal nano powder production equipment and preparing Carbon en capsulated nanomaterials Single, magnanimity prepares and the advantages that beneficial to industrialized production.Can as electrode of lithium cell negative material using the nano-powder of preparation To obtain the excellent properties such as height ratio capacity, high circulation life-span.
The content of the invention
For prior art deficiency and Improvement requirement, the present invention provides a kind of core-shell type carbon-clad metal sulfide nanometer and answered The preparation method and technology of particle is closed, using the carbon-clad metal nano particle of fabricated in situ as presoma, by cryogenic vulcanization Technique obtains carbon-clad metal sulfide nano-complex particle, and the nano-complex particle has graphitization carbon ball for shell, metal sulphur Compound is shell-caryogram nanostructured of core, improves Li insertion extraction capacity and cyclical stability：Effectively raise at big times Specific capacity under the conditions of rate discharge and recharge；Under the protection of graphitized carbon shell, electrode material structure is effectively safeguarded, improves electrode Stable circulation performance；760mAh/g reversible capacities can be obtained in lithium ion battery with nonaqueous electrolyte.
In order to achieve the above object, the equipment that the present invention uses sets to automatically control the production of direct-current arc metal nano powder Standby, technical scheme is:
Automatically control direct-current arc metal nano powder production equipment powder generate room anode on be put into block or Powder raw metal, and carbon source and inert gas are added, evaporated metal raw material, obtain carbon-clad metal nano particle forerunner Body.Then high pressure sealing reaction is put into after carbon-clad metal nano particle presoma is mixed with sulphur powder under the conditions of anhydrous and oxygen-free It is heat-treated in kettle, obtains carbon-clad metal sulfide nano composite material, specifically include following steps:
(1) 20~80g gold is added in the powder for automatically controlling direct-current arc metal nano powder production equipment generates room Category raw material, carbon source and inert gas, evaporated metal raw material obtain carbon covered metal nanoparticle precursor；
Described raw metal is positioned on the anode of powder generation room, and raw metal is iron, manganese, cobalt, nickel, copper, zinc, tin One or both of combination of the above, using block or powder；
When described carbon source is gaseous state, carbon source is methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene One or both of it is mixed above, 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 On the anode for generating room, carbon source is one kind and combinations thereof in ethanol, methanol or propyl alcohol, often add 5 in powder generates room~ 50ml carbon sources are passed through 0.01~0.03MPa inert gas；
When described carbon source is solid-state, it is placed on after carbon source and raw metal mixing briquetting on the anode of powder generation room, Carbon source is 1 with raw metal mass ratio:3~5:1；Carbon source is carbon and its allotrope, in glucose or polypyrrole (PPy) One kind and combinations thereof, it is 0.01MPa~0.06MPa to add inert gas volume；
Described inert gas is one kind of argon gas, helium or neon and combinations thereof；
(2) by carbon covered metal nanoparticle precursor anaerobic it is anhydrous under the conditions of mix with sulphur powder, be put into high pressure sealing In reactor, under inert gas shield, 200~500 DEG C are warming up to after 1~3h of solid phase reaction, room temperature is cooled to, obtains Carbon-clad metal sulfide nano-complex particle；
The condition of described anhydrous and oxygen-free is that water content is less than thousand a ten thousandths, and oxygen content is less than thousand a ten thousandths；
Described presoma and the mass ratio of sulphur powder are 1:1~1:3；
Described inert gas shield is that to be put into inert gas volume be 0.01MPa~0.08MPa；
Described inert gas is one kind of argon gas, helium, neon or nitrogen and combinations thereof；
The nano metal sulfide compound particle of above-mentioned preparation is used to prepare lithium-ion electric pole piece, vulcanizes in carbon-clad metal Amount of conductive agent and appropriate binding agent are added in thing nano-complex particle, is dispersed in solvent and obtains electrode material Material, described electrode material is applied to the single or double of conductive current collector, after solvent is removed under vacuum heating conditions, Various sizes of electrode slice is prepared according to battery specifications.
Described carbon-clad metal sulfide nano-complex particle and the mass percent of binding agent are 50~90:10；Lead The mass percent of electric agent is less than 40；
Described conductive agent is carbon black conductive agent (acetylene black, Super P, Super S, 350 G, carbon fiber (VGCF), carbon Nanotube (CNTs), Ketjen black (Ket jen black EC300J, Ket jen black EC300JD)) etc.), graphite One kind in agent (KS-6, SFG-6 etc.) or graphene and combinations thereof；
Described binding agent is polyvinylidene chloride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC), one kind of butadiene-styrene rubber (SBR) or polyvinyl alcohol (PVA) and combinations thereof；
Described solvent is 1-METHYLPYRROLIDONE (NMP), dinethylformamide (DMF) or deionized water；
Described conductive current collector is iron foil, nickel foil, aluminium foil, copper foil, foam copper, nickel foam, foamed aluminium or foamed iron.
Beneficial effects of the present invention are:
(1) preparation process is simple, low raw-material cost, does not produce harmful substance, can be with industrialized production；
(2) during preparing carbon-clad metal sulfide nano-complex particle, the presence of carbon shell can suppress metallic element Oxidation, the reunion of nano-particle is effectively prevented in heat treatment process；
(3) in heat treatment process, carbon shell provides the diffusion admittance that sulphur atom enters in core, makes sulphur atom and kernel gold Category reaction generation metal sulfide, is ultimately formed using core-shell type nano structure of the carbon as shell, metal sulfide for core；
(4) presence of graphitized carbon shell provides lithium ion exchanged passage, and carbon shell has very high intensity, effectively suppresses The volumetric expansion of metal sulfide, avoid metallic sulfide nano-particle because of Li insertion extraction process and caused by efflorescence and failure；
(5) sulfide has height ratio capacity in itself, and high lithium intercalation compound Li has been combined to form with lithium2S, graphitized carbon shell material Material provides more avtive spots and combined with lithium ion, forms LiC6Phase simultaneously has good circulation characteristic.Based on two kinds of materials Advantage, synthesized nano material have the comprehensive advantage such as height ratio capacity and high circulation stability.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates for the carbon coating iron sulfide nano-complex particle that embodiment 1 synthesizes.
Fig. 2 is the Raman spectrum (Raman) for the carbon coating iron sulfide nano-complex particle that embodiment 1 synthesizes.
Fig. 3 is charge and discharge of the carbon coating iron sulfide nano-complex particle of the synthesis of embodiment 1 under 500mA/g current density Electric curve.
Fig. 4 is circulation of the carbon coating artificial gold nano-complex particle of the synthesis of embodiment 1 under 500mA/g current density Stability curve.
Fig. 5 be embodiment it is 2-in-1 into carbon coating artificial gold nano-complex particle X-ray diffraction (XRD) collection of illustrative plates.
Fig. 6 be embodiment it is 2-in-1 into carbon coating artificial gold nano-complex particle Raman spectrum (Raman).
Embodiment
The present invention is further illustrated with reference to the accompanying drawings and detailed description.
Embodiment one:
About 40g iron blocks are taken to be put on the powder generation room anode for automatically controlling direct-current arc metal nano powder production equipment Evaporation, while ratio is passed through as 3:4 methane and argon gas, obtains carbon-encapsulated iron nanoparticles presoma；By this presoma in hand 2 are pressed in casing (ensureing anhydrous and oxygen-free environment):3 mass ratioes are put after being mixed with sulphur powder into high pressure sealing reactor, reaction Kettle is heated to 400 DEG C under the protection of 0.05MPa argon gas and carries out heat treatment 1.5h, is cooled to room temperature, obtains carbon coating iron sulfide and receive Nano composite material.
Above-mentioned carbon-clad metal sulfide nano composite material is fabricated to lithium-ion electric pole piece.Wherein electrode slice presses quality Carbon coating iron sulfide nano composite material, 10% Ketjen black and 10% polyvinylidene fluoride (PVDF) binding agent than 80% It is well mixed, appropriate 1-METHYLPYRROLIDONE (NMP) dissolving is added, slurry is coated on copper current collector electrode is made；This experiment Electrode 100 DEG C of dry 12h in vacuum drying oven, battery is assembled in high-purity argon gas atmosphere glove box.Wherein electrolyte is 1mol/ L LiPF6Solution, solvent are volume ratio 1:1 ethylene carbonate (EC) and diethyl carbonate (DC).It is right using polypropylene as barrier film Electrode is that lithium piece is assembled into CR2025 button cells.
The lithium ion battery negative electrode using carbon coating iron sulfide nano composite material as active material is made in the present invention, At room temperature, in the range of 0.01~3V, charge and discharge test is carried out to battery with 500mA/g current densities, obtains 760mAh/g specific volume Amount, stable cycle performance.
The XRD for the carbon coating iron sulfide nano composite material that embodiment one obtains is as shown in Figure 1.It is true by diffraction maximum in figure Iron sulfide and a small amount of unvulcanized simple substance iron phase are mainly contained in the fixed composite.
The Raman spectrum (Raman) for the carbon coating iron sulfide nano composite material that embodiment one obtains is as shown in Figure 2.By scheming The carbon that the relative intensity at middle D peaks and G peaks can determine to coat in the material is containing a large amount of defects.
In embodiment one, Fig. 3 and Fig. 4 are respectively at room temperature in the range of 0.01~3V, are entered with 500mA/g current density Capable charging and discharging curve and stable circulation performance curve.As seen from the figure, carbon coating vulcanization iron composite material produced by the present invention is made For lithium ion battery negative material when, there is the reversible specific capacity first close to 870mAh/g, Fig. 4 shows its cycle performance very It is stable.After the 50th circulation, its reversible specific capacity remains at 760mAh/g.
Embodiment two:
Take about 20g iron powders and 15g carbon dusts uniformly after mixing, be pressed into block and be put into and automatically control direct-current arc metal nano Evaporated on the anode of power production equipment powder generation room, while be passed through 0.06MPa helium, before obtaining carbon-encapsulated iron nanoparticles Drive body；This presoma is pressed 1 in glove box:3 mass ratioes are put after being mixed with sulphur powder into sealing reactor, and reactor exists 500 DEG C are heated under the protection of 0.01MPa nitrogen and carries out heat treatment 1h, are cooled to room temperature, it is nano combined to obtain carbon coating iron sulfide Material.
Embodiment three:
Take about 80g iron powders to be put into graphite crucible, add 20~40ml ethanol, graphite crucible is put into and automatically controlled directly Evaporated on the anode of the powder generation room of stream electric arc metal nano powder production equipment, while be passed through 0.01MPa neons and obtain carbon Encapsulated iron nanoparticles presoma；This presoma is pressed 1 in glove box:1 mass ratio is put after being mixed with sulphur powder to high pressure Seal in reactor, reactor is heated to 250 DEG C under the protection of 0.08MPa helium and carries out heat treatment 3h, is cooled to room temperature, obtains Carbon coating iron sulfide nano composite material.
Example IV:
About 20g block tin bodies are taken to be put into the anode for automatically controlling direct-current arc metal nano powder production equipment powder generation room Upper evaporation, while ratio is passed through as 4:1 methane and argon gas, obtain carbon covered stannum rice compound particle presoma；By this forerunner Body presses 1 in glove box:2 mass ratioes are put after being mixed with sulphur powder into high pressure sealing reactor, and reactor is in 0.02MPa nitrogen 450 DEG C are heated under gas shielded and carries out heat treatment 1.5h, is cooled to room temperature, obtains carbon coating artificial gold nano composite material.
The XRD for the carbon coating artificial gold nano composite material that example IV obtains is as shown in Figure 5.It is true by diffraction maximum in figure Artificial gold and a small amount of unvulcanized simple substance tin phase are mainly contained in the fixed composite.
The Raman spectrum (Raman) for the carbon coating artificial gold nano composite material that example IV obtains is as shown in Figure 6.By scheming The carbon that the relative intensity at middle D peaks and G peaks can determine to coat in the material is containing a large amount of defects.

Claims (4)

1. a kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle, it is characterised in that including following step Suddenly：
The first step, automatically control direct-current arc metal nano powder production equipment powder generate room in add raw metal, Carbon source and inert gas, evaporated metal raw material obtain carbon covered metal nanoparticle precursor；
Described raw metal is 20~80g, is placed on powder generation room anode；
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 generation room On anode, the inert gas that 5~50ml carbon sources are passed through 0.01~0.03MPa is often added in powder generates room；
When described carbon source is solid-state, be placed on after carbon source and raw metal mixing briquetting powder generation room anode on, carbon source with Metal-powder mass ratio is 1:3~5:1, it is 0.01MPa~0.06MPa to add inert gas volume；
Second step, carbon covered metal nanoparticle precursor is mixed with sulphur powder under the conditions of anhydrous and oxygen-free and is put into high pressure sealing reaction In kettle, under inert gas shield, after 200~500 DEG C of 1~3h of conditioned response, room temperature is cooled to, obtains carbon-clad metal sulphur Compound nano-complex particle；
Described anhydrous and oxygen-free is that water content is less than thousand a ten thousandths, and oxygen content is less than thousand a ten thousandths；
Described carbon covered metal nanoparticle precursor and the mass ratio of sulphur powder are 1:1~1:3；
Described raw metal is one or both of iron, manganese, cobalt, nickel, copper, zinc, tin combination of the above, using block or powder Body.
2. a kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle as claimed in claim 1, it is special Sign is, described gaseous carbon source be methane, ethane, acetylene, ethene, propylene, propine, propane, butane, one kind in butylene or Two or more mixing；Described liquid carbon source is one kind of ethanol, methanol or propyl alcohol and combinations thereof；Described solid-state carbon source is carbon And its allotrope, one kind in glucose or polypyrrole PPy and combinations thereof.
3. a kind of preparation method of core-shell type carbon-clad metal sulfide nano-complex particle as claimed in claim 1 or 2, its It is characterised by, the inert gas described in the first step is one kind of argon gas, helium or neon and combinations thereof；Described in second step Inert gas be one kind of argon gas, helium, neon or nitrogen and combinations thereof, the inert gas volume described in second step For 0.01MPa~0.08MPa.
4. a kind of any described core-shell type carbon-clad metal sulfide nano-complex particles of claim 1-3 be used to preparing lithium from Sub-electrode piece, it is characterised in that comprise the following steps：In carbon-clad metal sulfide nano-complex particle add conductive agent and Binding agent, it is dispersed in solvent and obtains electrode material；Electrode material is applied to the one side or double of conductive current collector Face, after solvent is removed under vacuum heating conditions, various sizes of electrode slice is prepared according to battery specifications；
Described carbon-clad metal sulfide nano-complex particle and the mass percent of binding agent are 50~90:10, conductive agent Mass percent be less than 40；
Described conductive agent is one kind of carbon black conductive agent, graphite agent or graphene and combinations thereof；
Described binding agent is polyvinylidene chloride PVDF, polytetrafluoroethylene PTFE, sodium carboxymethylcellulose CMC, butadiene-styrene rubber One kind of SBR or PVAC polyvinylalcohol and combinations thereof；
Described solvent is 1-METHYLPYRROLIDONE NMP, dinethylformamide DMF or deionized water；
Described conductive current collector is iron foil, nickel foil, aluminium foil, copper foil, foam copper, nickel foam, foamed aluminium or foamed iron.
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