CN105047878A - Method for preparing modified silicon-based anode material through vapor deposition - Google Patents

Method for preparing modified silicon-based anode material through vapor deposition Download PDF

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CN105047878A
CN105047878A CN201510415053.4A CN201510415053A CN105047878A CN 105047878 A CN105047878 A CN 105047878A CN 201510415053 A CN201510415053 A CN 201510415053A CN 105047878 A CN105047878 A CN 105047878A
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silicon
nano
amorphous carbon
negative material
prepared
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田东
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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
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0497—Chemical precipitation
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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 discloses a method for preparing a modified silicon-based anode material through vapor deposition. The method comprises the following steps: firstly, mixing nano silicon with a transition metal compound water solution, and heating the mixture until moisture evaporates; reducing the nano silicon which is loaded with a transition metal compound with a reducing agent; depositing the obtained nano silicon which is loaded with transition metal with an amorphous carbon source; and finally removing the transition metal on the nano silicon which is deposited with amorphous carbon by an acid medium solution. With the transition metal as a catalyst, the amorphous carbon is compounded with the nano silicon through chemical bonds; the amorphous carbon is deposited on the nano silicon, so as to obtain the composite anode material of the nano silicon and the amorphous carbon; the amorphous carbon has a porous structure; the volumetric expansion effect of the silicon powder generated in the charging and discharging processes can be effectively relieved; meanwhile, coating modification on each silicon powder particle can be uniformly carried out by vapor deposition; agglomeration of the nano silicon is avoided; and the cyclicity and the structure stability of the material are improved.

Description

The method of modified silicon based negative material is prepared in a kind of vapour deposition
Technical field
The invention belongs to field of lithium ion battery, particularly relate to a kind of negative material, be specifically related to a kind ofly utilize vapour deposition to deposit at silicon face one deck agraphitic carbon to carry out modification method to metallic silicon.
Background technology
Along with the development of automobile industry, oil, the exhaustion of the non-renewable fossil fuel such as natural gas receives publicity day by day, air pollution and room temperature effect also become global problem, and the fast development of national economy and the raising of living standards of the people, the dependency degree of China to crude oil grows with each passing day, Chinese energy safety is formed and directly threatened, in addition, the price fluctuation of crude oil also directly has influence on the development of Chinese national economy, along with constantly riseing of International Crude Oil, not only increase the economic pressures of middle national expenditures great number foreign exchange Imported oil, also domestic oil product market supply and demand contradiction is made more to give prominence in China's oil consumption structure, the oil of vehicles consumption accounts for over half, and present continuity significantly ascendant trend, these force people to have at searching new forms of energy, develop the quicken one's step development of electrokinetic cell and electric automobile of new vehicles aspect and be placed in more and more important position.Therefore, be more and more subject to people's attention with the secondary energy sources that green secondary cell is power, be considered to be the effective way solving lack of energy and environmental pollution.
Along with developing rapidly of the secondary energy sources being power with green secondary cell, various New-energy electric vehicle and portable electric appts, the widely using and high speed development of electric tool, also improve in succession to the requirement of chemical power source.Lithium ion battery because open circuit voltage is high, energy density is large, lightweight and self discharge is low etc., and advantage obtains increasingly extensive application in these fields.
At present, commercial lithium ion battery negative material is mainly graphite, and graphite has lower lithium embedding/deintercalation current potential, suitable reversible capacity and aboundresources, the advantage such as cheap, is more satisfactory lithium ion battery negative material.But its theoretical specific capacity only has 372mAh/g, thus limit the further raising of lithium ion battery specific energy, the demand of growing high-energy Portable power source can not be met.Meanwhile, when graphite is as negative material, in first charge-discharge process, form one deck solid electrolyte film (SEI) on its surface.Solid electrolyte film is the formation that react to each other such as electrolyte, negative material and lithium ion, irreversibly consumes lithium ion, is to form the main factor of of irreversible capacity; It two is in the process of Lithium-ion embeding, electrolyte easily and its be embedded in the process of moving out altogether, electrolyte is reduced, the gaseous product generated causes graphite flake layer to peel off, especially containing in the electrolyte of PC, graphite flake layer comes off new for formation interface, causes further SEI to be formed, irreversible capacity increases, and cyclical stability declines simultaneously.As lithium ion battery negative material, material with carbon element still exists that charge/discharge capacity is low, first cycle irreversible loss is large, solvent molecule intercalation and the shortcoming such as preparation cost is high altogether, and these are also the key issues solved needed in current Study on Li-ion batteries.
And silicon-based anode has unique advantage and potential, silicium cathode material, in charge and discharge process, can form Li with lithium 12si 7, Li 13si 4, Li 7si 3, Li 15si 4, Li 22si 5deng alloy, there is high power capacity (Li 22si 5the highest 4200mAh/g), the voltage of removal lithium embedded is low, advantage still studies discovery with electrolyte reactivity is low, security performance is good etc., when silica flour is as negative active core-shell material, in charge and discharge process, the change in volume of particle is very large, cause silicon grain efflorescence, the non-constant of electrode cycle.
Due to the bulk effect of silicon, researcher have employed the composite material of various silicon, as Si-Ni alloy, and SiCN/C ceramic composite, Ti-Si alloy, Si-TiN composite material, Cu 5si alloy, Ca 2si alloy and CrSi 2the materials such as alloy, or carry out produced with combination silicon carbon material with graphite separately, cycle performance obtains certain improvement but still not ideal enough.Except the composite material adopting silicon, researcher also attempts adopting nano-silicon to make silicon carbon material.As adopt magnetron sputtering or chemical deposition on a current collector deposit thin films of silicon method, adopt chemical vapour deposition (CVD) at graphite surface depositing nano silicon thin film, adopt nano Si-Ni alloy, adopt high-energy mechanical ball milling to make Si-C composite material or adopt particle mean size to be that the silica flour of 80 nanometers makes the methods such as Si-C composite material, these methods can improve the cycle performance of silicon really to a certain extent, but the limitation improved, the cycle performance of material still can not be satisfied the demand.
Summary of the invention
For prior art Problems existing, an object of the present invention is to provide to plant and utilizes vapour deposition agraphitic carbon to carry out the method for modification to silicium cathode material, and concrete steps are as follows:
A) by nano-silicon and transistion metal compound aqueous solution, carry out being heated to moisture evaporation, obtain the nano-silicon that load has transistion metal compound;
B) with reducing agent by described steps A) load that obtains has the nano-silicon of transistion metal compound to reduce, and obtains the nano-silicon that load has transition metal;
C) by amorphous carbon carbon source by described step B) load that obtains has the nano-silicon of transition metal to deposit, and obtains the nano-silicon depositing amorphous carbon;
D) utilize acid medium solution by described step C) in the transition metal on the nano-silicon of amorphous carbon of depositing that obtains remove, and carry out washing to neutrality, then dry, obtain modified Nano silicium cathode material.
Further, steps A) described in nano-silicon and the mass ratio of transistion metal compound be 100:(30 ~ 50).
Further, steps A) described in transistion metal compound comprise in the chloride of the chloride of nickel, the chloride of iron and cobalt one or more.
Further, steps A) described in the molar concentration of the transistion metal compound aqueous solution be preferably 0.05 ~ 0.3mol/L.
Further, steps A) described in heating-up temperature be 30 ~ 85 DEG C.
Further, step B) described in reducing agent be hydrogen.
Further, step C) described in amorphous carbon carbon source be gaseous hydrocarbons.
Further, step C) described in the temperature of deposition be 600 ~ 800 DEG C, the time of deposition is 2 ~ 5 hours, and the deposition of amorphous carbon accounts for 30 ~ 50% of nano-silicon weight.
Further, step D) described in acid medium solution be hydrochloric acid solution, molar concentration is 0.01 ~ 0.5mol/L.
A kind of agraphitic carbon that utilizes provided by the invention deposits the method for nano-silicon negative material being carried out to modification, using transition metal as catalyst, make to be combined with each other by chemical bond between amorphous carbon and nano-silicon, amorphous carbon is deposited on nano-silicon, obtain the composite negative pole material of nano-silicon and amorphous carbon, agraphitic carbon has loose structure, effectively can alleviate the Volumetric expansion that silica flour produces in discharge and recharge, vapour deposition simultaneously evenly can carry out coating modification to each silicon powder particle, avoid the reunion of nano-silicon, improve cyclicity and the structural stability of material.Experimental data shows, negative material provided by the invention gram specific capacity is used to reach 560mAh/g, the lithium ion battery prepared by this material is when charge and discharge cycles 500 times, capacity retention rate is more than 85%, illustrate that the lithium ion capacity storage rate using negative material provided by the invention to prepare is higher, there is good cycle performance.
Embodiment
In order to further illustrate the present invention, below in conjunction with embodiment, certain introduction is done to technical scheme of the present invention, but can not limiting the scope of the present invention be understood as.
Embodiment 1
According to nano-silicon: NiCl 2the mass ratio of=100:30, the NiCl of configuration 0.1mol/L 2the aqueous solution, then adds nano-silicon, at the temperature of 55 DEG C dispersed with stirring evenly, dry, obtaining area load has NiCl 2nano-silicon.With hydrogen, it is reduced again, obtain the nano-silicon that area load has W metal, pass into methane gas, make agraphitic carbon at nano-silicon surface deposition, the control time is 2h, and agraphitic carbon deposition accounts for 33% of nano-silicon weight, finally with the hydrochloric acid solution of 0.1mol/L, the W metal on nano-silicon is removed, and washing is to neutral, then dries, obtains modified Nano silicium cathode material.
Embodiment 2
According to nano-silicon: FeCl 3the mass ratio of=100:40, the FeCl of configuration 0.3mol/L 3the aqueous solution, then adds nano-silicon, at the temperature of 65 DEG C dispersed with stirring evenly, dry, obtaining area load has FeCl 3nano-silicon.With hydrogen, it is reduced again, obtain the nano-silicon that area load has metal Fe, pass into methane gas, make agraphitic carbon at nano-silicon surface deposition, the control time is 3h, and agraphitic carbon deposition accounts for 35% of nano-silicon weight, finally with the hydrochloric acid solution of 0.2mol/L, the metal Fe on nano-silicon is removed, and washing is to neutral, then dries, obtains modified Nano silicium cathode material.
Embodiment 3
According to nano-silicon: CoCl 3the mass ratio of=100:50, the CoCl of configuration 0.5mol/L 3the aqueous solution, then adds nano-silicon, at the temperature of 85 DEG C dispersed with stirring evenly, dry, obtaining area load has CoCl 3nano-silicon.With hydrogen, it is reduced again, obtain the nano-silicon that area load has metal Co, pass into methane gas, make agraphitic carbon at nano-silicon surface deposition, the control time is 5h, and agraphitic carbon deposition accounts for 45% of nano-silicon weight, finally with the hydrochloric acid solution of 0.3mol/L, the metal Co on nano-silicon is removed, and washing is to neutral, then dries, obtains modified Nano silicium cathode material.
Embodiment 4
According to nano-silicon: NiCl 2: FeCl 3the mass ratio of=100:20:20, the CoCl of configuration 0.2mol/L 3with the FeCl of 0.15mol/L 3the aqueous solution, then adds nano-silicon, at the temperature of 75 DEG C dispersed with stirring evenly, dry, obtaining area load has NiCl 2and FeCl 3nano-silicon.With hydrogen, it is reduced again, obtain the nano-silicon that area load has W metal and Fe, pass into methane gas, make agraphitic carbon at nano-silicon surface deposition, the control time is 3h, and agraphitic carbon deposition accounts for 39% of nano-silicon weight, finally with the hydrochloric acid solution of 0.2mol/L, the W metal on nano-silicon and Fe are removed, and washing is to neutral, then dries, obtains modified Nano silicium cathode material.
Comparative example 1
Undressed nano-silicon in embodiment 1.
Half-cell detects
For the electrical property of negative material prepared by inspection the inventive method, test by half-cell method of testing, negative material with above embodiment and comparative example: acetylene black: PVDF(Kynoar)=93:3:4(weight ratio), add appropriate NMP(N-methyl pyrrolidone) furnishing pulpous state, coat on Copper Foil, within 8 hours, make negative plate through vacuum 110 DEG C of dryings; Be to electrode with metal lithium sheet, electrolyte is 1mol/LLiPF6/EC+DEC+DMC=1:1:1, and microporous polypropylene membrane is barrier film, is assembled into battery.Charging/discharging voltage is 0 ~ 2.0V, and charge-discharge velocity is 0.2C, and carry out testing to battery performance, test result is in table 1.
Full battery testing
Negative material with embodiment and comparative example: SP:SBR(solid content 50%): CMC=94:2.5:1.5:2(weight ratio), add appropriate amount of deionized water and mix furnishing pulpous state, be applied on Copper Foil, at 90 DEG C, vacuumize drying; By LiCoO 2powder: SP:KS-6:PVDF=94:1.5:2:2.5(weight ratio), do after solvent evenly sizes mixing with NMP, be applied on aluminium foil, at 100 DEG C, vacuumize drying; By dried positive and negative electrode pole piece through roll-in, cut-parts, winding, fluid injection, sealing, formation process, make 18650 cylindrical batteries, barrier film is Celgard2400, electrolyte is 1MLiPF6 ∕ DMC:EC:DEC, use battery check device to carry out the detection of cycle performance, test result is in table 1.
The Performance comparision of negative material in the different embodiment of table 1 and comparative example
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.

Claims (8)

1. a method for modified silicon based negative material is prepared in vapour deposition, and its preparation process step is as follows:
A) by nano-silicon and transistion metal compound aqueous solution, carry out being heated to moisture evaporation, obtain the nano-silicon that load has transistion metal compound;
B) with reducing agent by described steps A) load that obtains has the nano-silicon of transistion metal compound to reduce, and obtains the nano-silicon that load has transition metal;
C) by amorphous carbon carbon source by described step B) load that obtains has the nano-silicon of transition metal to deposit, and obtains the nano-silicon depositing amorphous carbon;
D) utilize acid medium solution by described step C) in the transition metal on the nano-silicon of amorphous carbon of depositing that obtains remove, and carry out washing to neutrality, then dry, obtain modified Nano silicium cathode material.
2. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that steps A) in the mass ratio of nano-silicon and transistion metal compound be 100:(30 ~ 50).
3. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that steps A) in transistion metal compound comprise in the chloride of the chloride of nickel, the chloride of iron and cobalt one or more.
4. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that steps A) in heating-up temperature be 30 ~ 85 DEG C.
5. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that steps A) in reducing agent be hydrogen.
6. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that step C) in amorphous carbon carbon source comprise gaseous hydrocarbons.
7. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that step C) in deposition temperature be 600 ~ 800 DEG C, the time of deposition is 2 ~ 5 hours, and the deposition of amorphous carbon accounts for 30 ~ 50% of nano-silicon weight.
8. the method for modified silicon based negative material is prepared in a kind of vapour deposition according to claim 1, it is characterized in that step D) in acid medium solution be hydrochloric acid solution, molar concentration is 0.01 ~ 0.5mol/L.
CN201510415053.4A 2015-07-15 2015-07-15 Method for preparing modified silicon-based anode material through vapor deposition Pending CN105047878A (en)

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WO2017008615A1 (en) * 2015-07-15 2017-01-19 田东 Method for fabricating modified-silicon-based negative-electrode material by vapor deposition
CN107749470A (en) * 2017-10-17 2018-03-02 成都新柯力化工科技有限公司 A kind of Si/C layer structures negative active core-shell material and preparation method for lithium battery
CN114665083A (en) * 2022-03-21 2022-06-24 深圳市贝特瑞新能源技术研究院有限公司 Negative electrode material, preparation method thereof and lithium ion battery

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CN109942001B (en) * 2019-04-02 2022-08-09 骆驼集团武汉光谷研发中心有限公司 Silicon negative electrode material with spherical thorn-shaped structure and preparation method thereof
CN113629227B (en) * 2021-07-02 2022-07-12 中国长江三峡集团有限公司 Al2O3Synthesis method of/Al/Si nano composite material
CN116799178A (en) * 2023-06-19 2023-09-22 浙江锂宸新材料科技有限公司 Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery

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WO2017008615A1 (en) * 2015-07-15 2017-01-19 田东 Method for fabricating modified-silicon-based negative-electrode material by vapor deposition
CN107749470A (en) * 2017-10-17 2018-03-02 成都新柯力化工科技有限公司 A kind of Si/C layer structures negative active core-shell material and preparation method for lithium battery
CN114665083A (en) * 2022-03-21 2022-06-24 深圳市贝特瑞新能源技术研究院有限公司 Negative electrode material, preparation method thereof and lithium ion battery

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