CN108987724A - A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof - Google Patents

A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof Download PDF

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Publication number
CN108987724A
CN108987724A CN201810934858.3A CN201810934858A CN108987724A CN 108987724 A CN108987724 A CN 108987724A CN 201810934858 A CN201810934858 A CN 201810934858A CN 108987724 A CN108987724 A CN 108987724A
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hollow
negative pole
lithium ion
ion battery
composite negative
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赵亚
魏日兵
贲晴
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Zhejiang Hengyuan New Energy Technology Co Ltd
Shandong Forever New Energy Co Ltd
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Zhejiang Hengyuan New Energy Technology Co Ltd
Shandong Forever New Energy Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to hollow Si/C composite negative pole materials of a kind of lithium ion battery and preparation method thereof, belong to technical field of lithium batteries.In order to solve the problems, such as that volume expansion easily occurs in existing silica-base material and stability is poor, the preparation method for providing a kind of hollow Si/C composite negative pole material of lithium ion battery includes loading nanometic zinc oxide rod array template in the surface substrate of metal foil collector；Si nanometer stick array is grown on the surface of nanometic zinc oxide rod array template by rf magnetron sputtering；It is heat-treated under reducing atmosphere, obtains the Si nanometer stick array of load hollow form；Carbonization heat treatment is carried out under carbon source and atmosphere of inert gases makes carbon source decompose carbonization, and the Si nanometer stick array surface for being deposited on hollow form forms cladding.The present invention can effectively avoid Si material because of battery performance defect caused by volume expansion, improve stability, realize and improve specific capacity and stability, have excellent high rate performance and cycle performance.

Description

A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof
Technical field
The present invention relates to hollow Si/C composite negative pole materials of a kind of lithium ion battery and preparation method thereof, belong to lithium battery skill Art field.
Background technique
Lithium ion battery is a kind of novel Green Chemistry power supply, is had compared with traditional nickel-cadmium cell, nickel-metal hydride battery The advantage that voltage is high, the service life is long, energy density is big.From after nineteen ninety Sony Corporation of Japan release first generation lithium ion battery, it Various portable devices have been rapidly developed and be widely used in, the neck such as 3C Product, power device, energy storage device is related to Domain.Due to new-energy automobile flourish, the demand to power battery is increasing, the basis of power battery be have it is excellent The negative electrode material of charge-discharge performance.
Negative electrode material carries the effect of embedding and removing, and the quality of performance influences very the performance of lithium ion battery Greatly.Currently, negative electrode material is then selected from one of carbon-based material, lithium titanate, silica, silicon nanoparticle and Nanoalloy or several Kind, commercialized mainly graphite, but graphite electrode, since there are the growth questions of lithium dendrite arm, cell safety hidden danger is larger, and The embedding lattice dilatation with during removal lithium embedded is easy to cause graphite flake layer to remove and fall off to solvent altogether, leads to the appearance in cyclic process Amount decaying, to limit its service life.Therefore, numerous researchers is dedicated to developing novel negative electrode material, solution Certainly lithium dendrite growth bring security risk improves specific capacity and stability.
And compared to above-mentioned negative electrode material, the silicon based anode material of existing discovery, due to the quality capacity density of silicon, body Product capacity density and relatively low discharge voltage, all show high some commercial potential, thus instead of existing graphite material. In battery research, Si can form Li with Li4.4Si alloy, Theoretical Mass specific capacity can reach 4200mAh/g, volume and capacity ratio Respectively 1750mAh/cm3(being calculated according to the volume after Si extruding) and 9786mAh/cm3(according to the initial volume meter of Si It obtains).Although however, the quality capacity density of lithium alloy class material is very high, during actual embedding lithium takes off lithium, Its lattice will receive destruction, and 400% volume expansion occurs, this will will lead to the powdered of electrode, and pattern variation is eventually led to Occur expanding after embedding lithium or capacity is greatly reduced phenomena such as falling off, stability is poor and what cycle performance reduced lacks It falls into.
Summary of the invention
The present invention is directed to the above defect existing in the prior art, provides a kind of hollow Si/C composite negative pole of lithium ion battery Material and preparation method thereof solves the problems, such as it is how to avoid the volume expansion defect of silica-base material, improves silicon based anode material Stability and cycle performance.
An object of the present invention technical scheme is that, a kind of hollow Si/C of lithium ion battery is multiple The preparation method of negative electrode material is closed, method includes the following steps:
A, nanometic zinc oxide rod array template is loaded in the surface substrate of metal foil collector；
B, Si nanometer stick array is grown on the surface of nanometic zinc oxide rod array template by rf magnetron sputtering, is born Carry the metal foil collector of Si/ZnO composite nanorod array；
C, it under reducing atmosphere, is heat-treated under conditions of 400~800 DEG C, removes nanometic zinc oxide rod array template, Obtain the metal foil collector of the Si nanometer stick array of load hollow form；
D, carbonization heat treatment is carried out under carbon source and atmosphere of inert gases makes carbon source decompose carbonization, is deposited on the Si of hollow form Nanometer stick array surface forms cladding and obtains the hollow Si/C composite negative pole material of respective load after cooling.
The present invention loads nanometic zinc oxide rod array template in copper foil surface by first, then by rf magnetron sputtering at it Surface grows Si nanoparticle and forms Si nanometer stick array, in conjunction with using rf magnetron sputtering and in the zinc oxide nano loaded in advance The growth of rice stick surface, has morphology controllable, effect of uniform size is conducive to effective transmission of electronics, so that composite material table Reveal higher reversible specific capacity, the stability of guaranteed capacity；Handling using high temperature reduction makes to remove Si nanometer rods cladding ZnO nano-rod array template forms it into the Si nanometer rods of hollow structure, further changes its structure and morphology, is formed hollow The architectural characteristic of shape can make its when as lithium cell cathode material in process of intercalation inwardly or outwardly and meanwhile expansion space, Deformation buffer space is provided for its volume expansion, reduces and generates stress in its application process, the structure of stabilizing material, thus It is capable of forming the SEI film of the surface of stability；It is formed after the Si nanoparticle of hollow form again by making carbon source thermalization solution carbon at high temperature The Si nanoparticle surface changed in hollow form coats one layer of carbon, in this way, the ductility that can use carbon material plays buffering silicon substrate Outside volume expansion after the embedding lithium of material, and the sky that limitation Si material expands outward can be played by coating carbon material layer Between, greatly improve cyclical stability, it is thus also avoided that Si material directly contacts to form SEI film with electrolyte, realizes that improving silicon substrate bears The stability of pole material, reaches and increases substantially specific capacity and stability, has excellent high rate performance cycle performance；Meanwhile Coated with carbon material layer has high conduction performance, can be improved the conductivity and high rate performance of negative electrode material.
Reducing atmosphere one in the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, in step C As can preferably be formed to the purpose that ZnO is effectively restored, to realize that removal is more thorough in the presence of reducibility gas The architectural characteristic of empty shape.Preferably, reducing atmosphere described in step C is specially the mixed gas of hydrogen and inert gas.Energy It is enough adequately to restore ZnO, make the Si nanometer stick array by forming effective hollow form after subsequent high-temperature heat treatment, With preferable order and uniformity it is good.As further preferably, the volume ratio of the hydrogen and inert gas is 1: 7.0~10.Not only play the role of being effectively protected, but also zinc oxide can be made more preferably to be removed, effectively to change Si nanometer rods Appearance structure forms uniform hollow form architectural characteristic.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, described in step B The condition of rf magnetron sputtering are as follows:
Using HIGH-PURITY SILICON as target, at room temperature, air pressure is 1.5~3.0Pa, and radio-frequency power is 60~90W, sputtering time Continue 10~60min.It can make more sufficiently effective in the surface of zinc oxide nano rod growth silicon nano formation silicon nanometer Stick realizes and is evenly coated at the surface of ZnO nanorod template, provides uniform and orderly hollow form Si nanometer rods to be subsequent and provides Stability and reliability.Here HIGH-PURITY SILICON reaches 99.9% or more preferably with purity.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, described in step C The diameter of the Si nanometer rods of hollow form is 50~400nm, and the joint length of the Si nanometer rods of the hollow form is 0.1 μm~1 μm. It is capable of forming the of uniform size and good advantage of appearance structure characteristic by using magnetron sputtering, forms diameter and single to realize The controllable effect of length, advantageously forms stable cycle performance of battery.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, described in step C The temperature of heat treatment is 650~750 DEG C.ZnO nanorod mould material can be adequately removed, is advantageously formed uniform and stable The Si nanometer stick array of hollow form is conducive to preferably silicon materials be avoided the phenomenon that volume expansion occur, improves process of intercalation Stability avoids the occurrence of volume expansion and is broken or comes off.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, described in step D Carbon source is gaseous carbon source, and the gaseous carbon source is acetylene.Certainly, gaseous carbon source here can also use such as methane gaseousness The carbon source of matter.There is more evenly property using gaseous carbon source, the carbon formed in high temperature cabonization is made to be evenly distributed in hollow form Si nanometer stick array surface has integral coating homogeneity good, further raising stability.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, described in step D The temperature of carbonization heat treatment is 650~800 DEG C.Carbon source can be made, which to be more fully carbonized, to be made on the silicon nano surface of hollow form Carbon-coating is coated, the expansion of limitation silicon materials is played and there is better electric conductivity further preferably to make the carbon coated to be formed The thickness of layer reaches 5~30nm, has better cushion performance, and effective swelling volume expansion improves the stability of cathode, With high circulation performance.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, step C and step Inert gas described in D is independently selected from one or more of nitrogen, argon gas, helium, neon, Krypton and xenon.It mentions The stability of height heat treatment, avoids other side reactions from generating, and improves the validity of reduction and carbonization.
In the preparation method of the hollow Si/C composite negative pole material of above-mentioned lithium ion battery, preferably, described in step A Nanometic zinc oxide rod array template is obtained especially by following methods:
Copper foil current collector is dipped vertically into Zn (NO3)3■6H2The mixed aqueous solution of O and hexamethylenetetramine makes in copper foil table (the NO containing Zn in the load of face3)3■6H2O takes out copper foil current collector, after cleaning；It is put into tube furnace, is passed through inert protective gas, After 200~500 DEG C of high-temperature process, obtain loading nanometic zinc oxide rod array template on the surface substrate of copper foil.By adopting Nanoscale ZnO nanorod template can be effectively formed with hydro-thermal method, is conducive to be subsequently formed orderly, uniform Si nanometer rods Negative electrode material, and these raw materials are easy to get, and are more advantageous to industrialized production.
The second object of the present invention is to what is be achieved by the following technical programs, a kind of hollow Si/C of lithium ion battery is multiple Close negative electrode material, which is characterized in that the negative electrode material includes the Si nanometer rods of hollow form, the Si nanorod surfaces of the hollow form It is coated with carbon coating layer.
There is storage lithium activity by the hollow form silica-base material of internal layer, the anti-of insertion and deintercalation can occur with lithium ion Answer, realize the performance of high capacity, and more importantly by using the architectural characteristic of hollow form play alleviate embedding lithium when volume Stable material structure is realized in expansion, improves battery life；Meanwhile the carbon-coating of outer surface cladding had both had highly conductive characteristic, Can play the role of buffering again, make alleviate volume expansion face generate stress phenomena, avoid silicon-based nano particle rupture or The generation to fall off is conducive to keep battery capacity, realizes the cycle performance for improving battery.
In the above-mentioned hollow Si/C composite negative pole material of lithium ion battery, preferably, the Si nanometer of the hollow form Stick diameter is 50~400nm, preferably 100~230nm；It can also make the single maximum length of the Si nanometer rods of the hollow form 0.1~1 μm, preferably 0.4~0.6 μm；The carbon coating layer with a thickness of 5~30nm, preferably 10~20nm；Carbon-coating mass ratio For 5~30.0wt%, preferably 10~15wt%.With better circulating battery stability.
In conclusion compared with prior art, the present invention having the advantage that
The Si nanometer rods battle array that hollow form is capable of forming by the way of high temperature reduction is combined by using ZnO nanorod template Column, and be coated with carbon-coating on its surface realize and effectively avoid Si material because of battery performance defect caused by volume expansion, realization mentions The stability of high silicon based anode material, reaches and increases substantially specific capacity and stability, has excellent high rate performance and circulation Performance；Meanwhile coated with carbon material layer has high conduction performance, can be improved the conductivity and high rate performance of negative electrode material.
Detailed description of the invention
Fig. 1 is the preparation process flow schematic diagram of hollow Si/C composite negative pole material of the invention.
Fig. 2 is the cycle performance figure that hollow Si/C composite negative pole material of the invention is assembled into button cell as cathode.
Fig. 3 is the high rate performance figure that hollow Si/C composite negative pole material of the invention is assembled into button cell as cathode.
Specific embodiment
Below by specific embodiments and the drawings, the technical solutions of the present invention will be further described, but this Invention is not limited to these examples.
The hollow Si/C composite negative pole material of this lithium ion battery includes hollow Si nanometer stick array and surface by carbon-coating packet Cover, can also include make they load metal foil collector surface substrate on, the negative electrode material of formation be also equivalent to be Negative electrode of lithium ion battery.The copper foil surface that the Si nanometer stick array of the hollow form of formation is uniformly distributed, and have of uniform size Property it is good, make the appearance structure characteristic for the negative electrode material to be formed, can effectively play buffering silicon materials volume expansion defect, again Be conducive to improve capacity, make stability with higher and cycle performance, metal foil here can be copper foil or nickel foil etc., adopt The metal foil being process with conventional method.Further, preferably make the Si nanorod diameter about 50 of the hollow form to be formed~ 400nm, preferably 100~230nm, between most preferably 120~200nm；It can also make the joint length of the Si nanometer rods of hollow form Reach 0.1~1 μm, preferably 0.4~0.6 μm；Preferably making carbon-coating cladding therein is that amorphous carbon layer coats, then makes amorphous carbon Thickness degree is about 5~30nm, preferably 10~20nm.Preferably, make carbon-coating 5~30.0wt% of mass ratio, preferably 10~15wt%, It is equivalent to the percentage for the Si nanometer rods gross mass for making carbon-coating account for carbon-coating and hollow form, makes the negative electrode material to be formed that there is Si material Activity performance, meanwhile, the carbon coating layer for forming outer layer preferably guarantees that it makes to reach preferable slow with certain thickness Punching performance more effectively limits the volume expansion of Si material, is realized jointly with the architectural characteristic for forming hollow form from internal and outer Portion acts synergistically to limit the performance of its volume expansion, improves material capacity and stability, makes have the advantages that good cycle.
The hollow Si/C composite negative pole material of this lithium ion battery is added preferably with preparation process flow as shown in Figure 1 Work forms, and indicates direction process according to the arrow in Fig. 1, first using after over cleaning and smooth copper foil current collector is as substrate, The loading ZnO nanometer stick array on the substrate on its surface again, wherein ZnO nano-rod array preparation process is as follows: by above-mentioned process (area is 3 × 4cm to copper sheet after cleaning and being smooth2) immerse Zn (NO3)3■6H2O and hexamethylenetetramine mixed aqueous solutions Middle immersion is abundant, here Zn (NO3)3■6H2The specific dosage of O and hexamethylenetetramine can be adjusted according to the actual situation, After handling 1~4h preferably under 60~90 DEG C of water bath conditions, copper sheet is further taken out, is rinsed with a large amount of deionized waters；Finally, being put into pipe It in formula furnace, is passed through under the protective atmosphere of the inert gases such as argon gas, nitrogen, controls temperature in 200~500 DEG C of 1~4h of heat preservation, obtain Nanometic zinc oxide rod array is loaded on the surface substrate of copper foil；Again in the copper foil of above-mentioned loading ZnO nanometer stick array through radio frequency Magnetron sputtering makes to grow to form Si nanometer rods on surface in the surface of ZnO nanorod sputtering Si, and obtaining load, Si/ZnO is compound receives The copper foil of rice stick array, then, by reducibility gas H2Under the mixing reducing atmosphere of Ar (volume ratio 1:9), 400~ 800 DEG C of 2~8h of heat treatment remove ZnO nano-rod array template, obtain the Si nanometer stick array of hollow form；Using carbon coating mistake With 5 under mixed gas (volume ratio 1:9) atmosphere of journey, specially acetylene or the inert gases such as other gaseous carbon sources and nitrogen DEG C/rate of min is warming up to 650 DEG C~800 DEG C and keeps the temperature 2~6h, cooled to room temperature obtains corresponding product.More than Inert nitrogen gas can also carry out generations using mixing one or more of in nitrogen, helium, neon, argon gas, Krypton and xenon It replaces.It is also seen that being capable of forming the hollow form structure spy that uniformity is good and has the Si nanometer stick array filled, and is formed from Fig. 1 Property is more apparent.
Embodiment 1
By the copper foil current collector after over cleaning peace is whole, (area is 3 × 4cm2) be dipped vertically into containing 1.78g Zn (NO3)3■6H2The 200mL aqueous solution that O is mixed with 0.84g hexamethylenetetramine, then temperature is controlled under 90 DEG C of water bath condition After isothermal holding 2h, it can make to form film layer on the surface of smooth copper foil current collector, take out copper foil current collector, first with largely going After ionized water rinses；Then, it is put into tube furnace, is passed through argon gas as protective gas, controls hot conditions of the temperature at 400 DEG C Under carry out heat preservation 2h, obtain loading upper nanometic zinc oxide rod array template in the surface substrate of copper foil current collector；
It is 2Pa, power 80W, through radio frequency magnetron in room temperature and air pressure again using HIGH-PURITY SILICON (purity >=99.9%) as target 40min is sputtered, makes to sputter Si nanoparticle on the surface of above-mentioned ZnO nano-rod array template, makes to grow Si nanometers on its surface Particle forms Si nanometer rods, obtains the copper foil current collector of load Si/ZnO composite nanorod array；Then, by H2With Ar (H2With The volume ratio of Ar be 1:9) mixing reducing atmosphere under, and control temperature carried out under conditions of 600 DEG C heat treatment 4h make to remove ZnO nano-rod array template obtains the copper foil current collector of the Si nanometer stick array of load hollow form；So that the Si of hollow form is received here The diameter of rice stick is 100~150nm, and joint length reaches 0.4~0.6 μm；
Again under mixed gas (volume ratio of both acetylene and nitrogen is 1:9) atmosphere of acetylene and nitrogen, and with 5 DEG C/ The rate of min, which is warming up to 650 DEG C and keeps the temperature, carries out carbonization heat treatment 3h, so that acetylene gas is decomposed carbonization, is deposited on hollow form Si nanometer stick array surface forms cladding and forms amorphous carbon coating layer, makes the thickness of amorphous carbon coating layer in 10~20nm, Using cooled to room temperature, taking-up obtains corresponding hollow Si/C composite negative pole material.
The storage lithium performance of the present embodiment corresponding Si/C composite Nano negative electrode material obtained above is subjected to characterization use The button-shaped half-cell of CR2025 is cut to the Si/C composite nano materials of suitable dimension as working electrode, is lithium piece to electrode, Polypropylene-three layers of porous septum of polyethylene-polypropylene (PP-PE-PP) that diaphragm uses with a thickness of 25 μm, electrolyte are 1M hexafluoro The ethylene carbonate (Ethylene carbonate, EC) and dimethyl carbonate (Dimethylcarbonate, DMC) of lithium phosphate Mixed solution (EC:DMC=1:1, v/v).The voltage window of charge and discharge cycles be 0.07V~3.0V, 0.05~10C of electric current into Row cyclic voltammetry and charge-discharge magnification test.Specific test result is as Figure 2-3, it can be seen from the figure that using The respective negative material cyclical stability with higher and charge-discharge magnification performance that method of the invention obtains, specifically from Fig. 2 In as can be seen that after 800 circulations, capacity retention ratio still is able to reach 94% or more, capacity reach 1800Amh g with On.From fig. 3 it can also be seen that in 0.5C, 1C, 2C, under the current condition of 4C, capacity is 1500mAh g-1,1250mAh g-1, 1000mAh g-1,800mAh g-1Left and right；And when current density returns to 0.5C from 4C, the capacity of material can be restored to 1400mAh g-1Left and right, illustrates the excellent high rate performance of material and good cycle performance.
Embodiment 2
By the copper foil current collector after over cleaning peace is whole, (area is 3 × 4cm2) be dipped vertically into containing 1.78g Zn (NO3)3■6H2The 200mL aqueous solution that O is mixed with 0.84g hexamethylenetetramine, then temperature is controlled under 90 DEG C of water bath condition After isothermal holding 2h, it can make to form film layer on the surface of copper foil current collector, copper foil current collector be taken out, first with a large amount of deionization After water rinses；Then, be put into tube furnace, be passed through argon gas as protective gas, control temperature under 500 DEG C of hot conditions into Row heat preservation 2h obtains loading upper nanometic zinc oxide rod array template in the surface substrate of copper foil current collector；
It is 3Pa, power 90W, through radio frequency magnetron in room temperature and air pressure again using HIGH-PURITY SILICON (purity >=99.9%) as target 30min is sputtered, makes to sputter Si nanoparticle on the surface of above-mentioned ZnO nano-rod array template, makes to deposit Si nanometers on its surface Particle obtains the copper foil current collector of load Si/ZnO composite nanorod array；Then, by H2With helium (H2With the volume of helium Than under the mixing reducing atmosphere for 1:9), and controls temperature and carry out heat treatment 3h under conditions of 750 DEG C and make to remove ZnO nanorod Array mould plate obtains the copper foil current collector of the Si nanometer stick array of load hollow form；Here the diameter of the Si nanometer rods of hollow form For 150~200nm, joint length reaches 0.4~0.5 μm；
Again under mixed gas (volume ratio of both acetylene and argon gas is 1:9) atmosphere of acetylene and argon gas, and with 8 DEG C/ The rate of min, which is warming up to 750 DEG C and keeps the temperature, carries out carbonization heat treatment 2h, so that acetylene gas is decomposed carbonization, is deposited on hollow form Si nanometer stick array surface forms cladding and forms amorphous carbon coating layer, makes the thickness of amorphous carbon coating layer in 5~10nm, then By cooled to room temperature, taking-up obtains corresponding hollow Si/C composite negative pole material.
The storage lithium performance of the present embodiment corresponding Si/C composite Nano negative electrode material obtained above is subjected to characterization use The button-shaped half-cell of CR2025, specific assembling mode and performance test methods are consistent with embodiment 1, and which is not described herein again.It surveys Test result can reach and the comparable cycle performance of embodiment 1 and high rate performance effect.
Embodiment 3
The specific of upper nanometic zinc oxide rod array template is loaded for the surface substrate in copper foil current collector in the present embodiment It is consistent that the preparation method is the same as that of Example 1, and which is not described herein again, obtains loading upper zinc-oxide nano in the surface substrate of copper foil current collector It is 1.5Pa, power 60W, warp in room temperature and air pressure after stick array mould plate, then using HIGH-PURITY SILICON (purity >=99.9%) as target Rf magnetron sputtering 60min makes to sputter Si nanoparticle on the surface of above-mentioned ZnO nano-rod array template, and it is heavy on its surface to make Product Si nanoparticle, obtains the copper foil current collector of load Si/ZnO composite nanorod array；Then, by H2With helium (H2With helium The volume ratio of gas be 1:8) mixing reducing atmosphere under, and control temperature carried out under conditions of 800 DEG C heat treatment 3h make to remove ZnO nano-rod array template obtains the copper foil current collector of the Si nanometer stick array of load hollow form；Here the Si nanometer of hollow form The diameter of stick is 200~230nm, and joint length reaches 0.5~0.6 μm；
Again under mixed gas (volume ratio of both acetylene and argon gas is 1:9) atmosphere of acetylene and argon gas, and with 10 DEG C/ The rate of min, which is warming up to 800 DEG C and keeps the temperature, carries out carbonization heat treatment 2h, so that acetylene gas is decomposed carbonization, is deposited on hollow form Si nanometer stick array surface forms cladding, makes the thickness of amorphous carbon coating layer in 15~25nm, now by naturally cooling to room Temperature, taking-up obtain corresponding hollow Si/C composite negative pole material.
The storage lithium performance of the present embodiment corresponding Si/C composite Nano negative electrode material obtained above is subjected to characterization use The button-shaped half-cell of CR2025, specific assembling mode and performance test methods are consistent with embodiment 1, and which is not described herein again.It surveys Test result can reach and the comparable cycle performance of embodiment 1 and high rate performance effect.
Embodiment 4
The specific of upper nanometic zinc oxide rod array template is loaded for the surface substrate in copper foil current collector in the present embodiment It is consistent that the preparation method is the same as that of Example 1, and which is not described herein again, obtains loading upper zinc-oxide nano in the surface substrate of copper foil current collector It is 2.0Pa, power 80W, warp in room temperature and air pressure after stick array mould plate, then using HIGH-PURITY SILICON (purity >=99.9%) as target Rf magnetron sputtering 50min makes to sputter Si nanoparticle on the surface of above-mentioned ZnO nano-rod array template, makes raw on its surface Long Si nanoparticle forms Si nanometer stick array, obtains the copper foil current collector of load Si/ZnO composite nanorod array；Then, it passes through Cross H2With argon gas (H2Be 1:7 with the volume ratio of argon gas) mixing reducing atmosphere under, and control temperature under conditions of 400 DEG C into Row heat treatment 8h makes to remove ZnO nano-rod array template, obtains the copper foil current collector of the Si nanometer stick array of load hollow form；This In the diameter of Si nanometer rods of hollow form be 50~100nm, joint length reaches 0.5~0.6 μm；
Again under mixed gas (volume ratio of both acetylene and argon gas is 1:10) atmosphere of acetylene and argon gas, and with 15 DEG C/rate of min is warming up to 700 DEG C and keeps the temperature and carry out carbonization heat treatment 4h, so that acetylene gas is decomposed carbonization, is deposited on hollow form Si nanometer stick array surface formed and coat to obtain amorphous carbon coating layer, make the thickness of amorphous carbon coating layer in 15~30nm, Using cooled to room temperature, taking-up obtains corresponding hollow Si/C composite negative pole material.
The storage lithium performance of the present embodiment corresponding Si/C composite Nano negative electrode material obtained above is subjected to characterization use The button-shaped half-cell of CR2025, specific assembling mode and performance test methods are consistent with embodiment 1, and which is not described herein again.It surveys Test result can reach and the comparable cycle performance of embodiment 1 and high rate performance effect.
Specific embodiment described in the present invention only illustrate the spirit of the present invention by way of example.The neck of technology belonging to the present invention The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
It is skilled to this field although present invention has been described in detail and some specific embodiments have been cited For technical staff, as long as it is obvious for can making various changes or correct without departing from the spirit and scope of the present invention.

Claims (10)

1. a kind of preparation method of the hollow Si/C composite negative pole material of lithium ion battery, which is characterized in that this method includes following Step:
A, upper nanometic zinc oxide rod array template is loaded in the surface substrate of metal foil collector；
B, Si nanometer stick array is grown on the surface of nanometic zinc oxide rod array template by rf magnetron sputtering, is loaded The metal foil collector of Si/ZnO composite nanorod array；
C, it under reducing atmosphere, is heat-treated under conditions of 400~800 DEG C, removes nanometic zinc oxide rod array template, obtain Load the metal foil collector of the Si nanometer stick array of hollow form；
D, carbonization heat treatment is carried out under carbon source and atmosphere of inert gases makes carbon source decompose carbonization, is deposited on the Si nanometer of hollow form Stick array surface forms cladding and obtains the hollow Si/C composite negative pole material of respective load after cooling.
2. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery according to claim 1, which is characterized in that step Reducing atmosphere described in rapid C is specially the mixed gas of hydrogen and inert gas.
3. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery according to claim 2, which is characterized in that institute The volume ratio for stating hydrogen and inert gas is 1:7.0~10.
4. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery according to claim 1, which is characterized in that step The condition of rf magnetron sputtering described in rapid B are as follows:
Using HIGH-PURITY SILICON as target, at room temperature, air pressure is 1.5~3.0Pa, and radio-frequency power is 60~90W, and sputtering time is lasting 10~60min.
5. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery described in -4 any one according to claim 1, It is characterized in that, the diameter of the Si nanometer rods of hollow form described in step C is 50~400nm, the Si nanometer rods of the hollow form Joint length is 0.1 μm~1 μm.
6. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery described in -4 any one according to claim 1, It is characterized in that, the temperature of heat treatment described in step C is 650~750 DEG C.
7. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery according to claim 1, which is characterized in that step Carbon source described in rapid D is gaseous carbon source, and the gaseous carbon source is acetylene.
8. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery according to claim 1, which is characterized in that step The temperature of heat treatment of being carbonized described in rapid D is 650~800 DEG C.
9. the preparation method of the hollow Si/C composite negative pole material of lithium ion battery according to claim 2, which is characterized in that step Inert gas described in rapid C and step D is independently selected from one of nitrogen, argon gas, helium, neon, Krypton and xenon Or it is several.
10. a kind of hollow Si/C composite negative pole material of lithium ion battery, which is characterized in that the negative electrode material includes the Si of hollow form The Si nanorod surfaces of nanometer rods, the hollow form are coated with carbon coating layer.
CN201810934858.3A 2018-08-16 2018-08-16 A kind of hollow Si/C composite negative pole material of lithium ion battery and preparation method thereof Pending CN108987724A (en)

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CN111229287A (en) * 2020-03-25 2020-06-05 吉林师范大学 Carbon fiber cloth load tubular g-C3N4Photocatalytic material and preparation method thereof
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CN110931720A (en) * 2019-04-02 2020-03-27 西安翱宇科技管理咨询合伙企业(有限合伙) Low-cost preparation method of high-compaction-density negative electrode material for lithium ion battery
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CN111740078A (en) * 2019-10-21 2020-10-02 中国科学院深圳先进技术研究院 Manufacturing method of lithium ion battery cathode structure and lithium ion battery cathode structure
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CN111229287B (en) * 2020-03-25 2022-10-21 吉林师范大学 Carbon fiber cloth load tubular g-C 3 N 4 Photocatalytic material and method for producing same

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