CN104466185A - Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof - Google Patents

Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof Download PDF

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CN104466185A
CN104466185A CN201410635908.XA CN201410635908A CN104466185A CN 104466185 A CN104466185 A CN 104466185A CN 201410635908 A CN201410635908 A CN 201410635908A CN 104466185 A CN104466185 A CN 104466185A
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silicon
nano
carbon
cathode materials
lithium ion
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唐永炳
李文跃
李振声
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a silicon/carbon negative electrode composite material and a preparation method thereof as well as a lithium ion battery and a negative electrode thereof. The silicon/carbon negative electrode composite material is of a core-shell coating structure which takes nanometer silicon particles as a core and in-situ carbon as a shell, and gas are formed between the nano silicon particles and the in-situ carbon shell. The preparation method of the silicon/carbon negative electrode composite material comprises the following steps: preparing an organic carbon source SiO2-coated composite material, performing pre-oxidation treatment on the organic carbon source SiO2-coated composite material, and performing in-situ carburization, SiO2 magnesiothermic reduction reaction and the like on the organic carbon source SiO2-coated composite material subjected to pre-oxidation treatment. A lithium ion battery negative electrode and the lithium ion battery respectively contain the silicon/carbon negative electrode composite material, and the lithium ion battery is endowed with favorable cycle performance and rate performance. The silicon/carbon negative electrode composite material has excellent conductivity and a structure stability performance, and the preparation method is safe and environment-friendly, and suitable for industrial production.

Description

Silicon/carbon compound cathode materials and preparation method thereof, lithium ion battery and negative pole thereof
Technical field
The invention belongs to technical field of lithium batteries, be specifically related to a kind of silicon/carbon compound cathode materials and preparation method thereof, lithium ion battery, lithium ion battery negative.
Background technology
At present, in worldwide, lithium ion battery is used in communication, traffic, computer and other all trades and professions more and more, and the life for people provides countless facility.And along with growth in the living standard, people pay close attention to resource, environment, security problems more.Lithium ion battery mainly comprises positive pole, electrolyte and negative pole three parts.The electrode material of lithium ion battery is for improving the chemical property of battery and the aspect such as to reduce costs most important.
Wherein, traditional lithium cell cathode material is made up of graphite, and the lithium storage content of graphite can only reach ~ 300mAh/g.Along with high-power lithium battery applying in fields such as communication base stations, higher, the safer electrode material of searching capacity becomes the top priority of lithium battery development.Silicon is as a kind of new lithium cell cathode material, and 10 times of its lithium storage content nearly graphite, reach 3000mAh/g.The discharge platform of conventional graphite negative pole is only than lithium metal height 10-20 millivolt, through repeatedly Lithium-ion embeding and deintercalation, lithium ion easily assembles formation lithium metal dendrite arm at Carbon anode, these dendrite arms may pierce through only has the polymer insulation barrier film of tens micron thickness to form short circuit, and then the potential safety hazard such as cause that burning is even exploded.Silicon is as its discharge platform of negative material than lithium metal mean height about 200 millivolts, and lithium ion cannot form lithium metal dendrite, so silicon is also more superior than the security performance of graphite as negative material at negative pole under the current potential that this is higher.
But also be there is certain technical problem as negative material in osmanthus at present, due to silica-base material poorly conductive, serious volumetric expansion is there is in removal lithium embedded process, cause coming off of the efflorescence of material and whole electrode, therefore, in the technical difficult points of lithium ion battery applications, silicium cathode material is that in the process of most silica-base material in embedding lithium and deintercalation, change in volume is huge, like this after circulation several times, the structure of material expands, loose, finally cause electricity loose contact, capacity acutely fails.
Along with the development of nanometer technology, nanometer technology penetrates into field of lithium ion battery material preparation, prepare nanofiber, nanotube, nano-powder technology more and more ripe.Nano material due to size little, local volume expansion obviously declines, and effectively maintains the integrality of material in charging and discharging process, and nanometer technology will be solve the important channel and direction that silicium cathode material structure expands.Adopt the method for chemical vapour deposition (CVD) (CVD) successfully to prepare if any people and there is Si nano-material and hollow nano silicon ball material.Somebody adopts the method for electrostatic spinning to prepare and provides siliceous complex fiber material, shows good cycle performance of lithium ion battery and high rate performance.Somebody adopts surface modification technology to prepare siliceous complex fiber material, also shows excellent lithium electricity battery performance.But there is more weak point preparing in Si-based nanometer material process in above method, such as preparation process is complicated, the prices of raw and semifnished materials are expensive and with higher toxicity (method of vapour deposition is prepared silicon materials and will be used inflammable and explosive and have silane or the silicon tetrachloride material of hypertoxicity), be difficult to large-scale commercial production etc., and prepared composite material containing silicon is still undesirable for solution structure expansion issues, still easily causes battery capacity obviously to fail.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, negative material Stability Analysis of Structures, conductivity are high to provide one effectively to ensure, and silicon/carbon compound cathode materials of preparation method's safety and environmental protection and preparation method thereof.
Another object of the present invention is to provide a kind of negative pole structure to stablize, the lithium ion battery that the stability capacitance in cycle charge discharge electric process is high and lithium ion battery negative.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
A kind of silicon/carbon compound cathode materials, it is is core with silicon nanoparticle, take in-situ carbon as the nucleocapsid clad structure of shell, and has space between described silicon nanoparticle and described in-situ carbon housing.
And a kind of silicon/carbon compound cathode materials preparation method, comprises the steps:
In a solvent, by the Nano-meter SiO_2 of surface through functionalization 2mix with organic carbon source, make described organic carbon source be coated on described Nano-meter SiO_2 2surface, after desolventizing, obtains organic carbon source coated Si O 2composite material;
By described organic carbon source coated Si O 2composite material adopt step heat up method carry out pre-oxidation treatment;
In reducing atmosphere, by the described organic carbon source coated Si O after described pre-oxidation treatment 2composite material and magnesium at 600-800 DEG C, carry out in-situ carburization and SiO 2magnesiothermic reduction reaction, after question response terminates, carry out pickling.
And, a kind of lithium ion battery negative, comprise collector and be combined on described collector containing the active layer of negative material, described negative material is silicon/carbon compound cathode materials of preparing of above-mentioned silicon/carbon compound cathode materials preparation method or silicon/carbon compound cathode materials described above.
And a kind of lithium ion battery, described lithium ion battery comprises above-mentioned lithium ion battery negative.
Compared with prior art, above-mentioned silicon/carbon compound cathode materials adopts nano-silicon as nucleome, adopts in-situ carbon as housing, makes silicon/carbon compound cathode materials on the basis with high lithium storage content, have excellent electric conductivity by carbon clad structure.By the space existed between nano-silicon nucleome and carbon housing, for nano-silicon volumetric expansion retains cushion space in removal lithium embedded process, thus effectively ensure that the Stability Analysis of Structures performance of silicon/carbon compound cathode materials.
Upper silicon/carbon compound cathode materials preparation method is by Nano-meter SiO_2 2surface-functionalized process, effectively can be combined in its surface and form nucleocapsid clad structure, make Nano-meter SiO_2 by magnesiothermic reduction reaction by carbon source 2be reduced into nano-silicon, volume shrinks in the process, thus forms certain space in carbon shell, and these spaces can provide effective space for the expansion of silicon materials, ensures material structural stability in lithium ion deintercalation process.The carbon shell that in-situ carburization is formed has good conductivity, improves cyclical stability and the high rate performance of silicon/carbon compound cathode materials further.In addition, this silicon/carbon compound cathode materials preparation method uses the prices of raw and semifnished materials cheap and non-toxic, and safety and environmental protection, is suitable for industrial production, effectively reduces production cost.
Above-mentioned lithium ion battery negative is due to containing above-mentioned silicon/carbon compound cathode materials, again because this silicon/carbon compound cathode materials can have structural stability and good conductivity as above, therefore, in the course of the work, this lithium ion battery negative electrode structure stability, lithium storage content is high.
Above-mentioned lithium ion battery is due to containing above-mentioned lithium ion battery negative, then this lithium ion battery follows in discharge and recharge and recycles in process for a long time, and lithium ion battery is had good cycle performance and high rate performance.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is embodiment of the present invention silicon/carbon compound cathode materials preparation method flow chart;
The silicon that Fig. 2 provides for the embodiment of the present invention 1/carbon compound cathode materials scanning electron microscope (SEM) photograph and projection Electronic Speculum figure; Wherein, silicon/carbon compound cathode materials scanning electron microscope (SEM) photograph of providing for embodiment 1 of Fig. 2 a; The silicon that Fig. 2 b provides for embodiment 1/carbon compound cathode materials projection Electronic Speculum figure;
The cycle performance of lithium ion battery resolution chart of silicon/carbon compound cathode materials that Fig. 3 provides for the employing embodiment of the present invention 1;
The lithium ion battery high rate performance resolution chart of silicon/carbon compound cathode materials that Fig. 4 provides for the employing embodiment of the present invention 1.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Example of the present invention provides a kind of Environmental Safety, and can prepare the preparation method of constitutionally stable silicon/carbon compound cathode materials.This silicon/carbon compound cathode materials preparation method technological process refers to Fig. 1, and it comprises the steps:
Step S01. prepares organic carbon source coated Si O 2composite material:
In a solvent, by the Nano-meter SiO_2 of surface through functionalization 2mix with organic carbon source, make described organic carbon source be coated on described Nano-meter SiO_2 2surface, after desolventizing, obtains organic carbon source coated Si O 2composite material;
Step S02. is to organic carbon source coated Si O 2composite material carries out pre-oxidation treatment:
By organic carbon source coated Si O in step S01 2composite material adopt step heat up method carry out pre-oxidation treatment;
Step S03. is to the organic carbon source coated Si O after pre-oxidation treatment 2composite material carries out in-situ carburization and SiO 2magnesiothermic reduction reaction:
In reducing atmosphere, by the described organic carbon source coated Si O after pre-oxidation treatment in step S02 2composite material and magnesium at 600-800 DEG C, carry out in-situ carburization and SiO 2magnesiothermic reduction reaction, after question response terminates, carry out pickling.
Particularly, in above-mentioned steps S01, surface is through the Nano-meter SiO_2 of functionalization 2carry out, in mixed process, passing through Nano-meter SiO_2 with organic carbon source 2the effect of the functional group on surface, makes organic carbon source adsorb and is combined in Nano-meter SiO_2 2surface.
In one embodiment, this surface is through the Nano-meter SiO_2 of functionalization 2carry out in mixed process with organic carbon source, temperature controls at 80-140 DEG C, and in this temperature range, making both, fully mixing is until even, and in an embodiment, the time controling of both mixed processing is at 2-10 hour.In one embodiment, this surface is through the Nano-meter SiO_2 of functionalization 2carrying out mixing with organic carbon source is stir 5 hours at 80 DEG C.By the control of temperature and time, organic carbon source is made effectively to adsorb and be combined in Nano-meter SiO_2 2surface.
In another embodiment, this surface is through the Nano-meter SiO_2 of functionalization 2be 1:(1-5 with organic carbon source according to mass ratio) ratio mix, by the ratio both controlling, effectively can control Nano-meter SiO_2 2the amount of surface coated carbon source, thus final thickness and the amount ratio controlling in-situ carbon housing, to realize the electric conductivity and the Stability Analysis of Structures performance that provide silicon/carbon compound cathode materials.
In another embodiment, this organic carbon source selects the mixture of any one or more in polyacrylonitrile (PAN), polyvinyl alcohol, polypyrrole.
In one embodiment, this Nano-meter SiO_2 2the method of surface-functionalized process as follows:
In a solvent, by Nano-meter SiO_2 2with silane coupler according to mass ratio 100:(1-5) ratio carry out mixed processing 2-10 hour.By silane coupler and control its addition can effectively to Nano-meter SiO_2 2surface is modified, and makes its surface be connected with functional group.
Wherein, in one embodiment, this silane coupler selects the mixture of any one or more in aminopropyl triethoxysilane (APTES), N-(β-aminoethyl)-gamma-aminopropyl-triethoxy-silane (KH-791), vinyltriethoxysilane (KH-151).Those silane couplers can effectively to Nano-meter SiO_2 2modifying surface, makes SiO 2surface conjunction just like hydroxyl functional groups, thus can effectively adsorb carbon source, and carbon source is effectively evenly combined in Nano-meter SiO_2 2surface, forms carbon source coating layer.
In one embodiment, the Nano-meter SiO_2 in the various embodiments described above 2select Nano-meter SiO_2 2ball or Nano-meter SiO_2 2one or both mixture in hollow pipe.In a further embodiment, this Nano-meter SiO_2 2ball or Nano-meter SiO_2 2hollow pipe adopts the method for sol-gel to prepare.
In one embodiment, this Nano-meter SiO_2 2ball can prepare according to step S11a in such as Examples below 1.
In the various embodiments described above, this Nano-meter SiO_2 2the diameter control of ball is at 50nm-300nm.If adopt as step S11a in embodiment 1 prepares, can by the ratio regulation and control Nano-meter SiO_2 to ethanol, water, ammoniacal liquor, tetraethyl orthosilicate 2bulb diameter.
In another specific embodiment, this Nano-meter SiO_2 2hollow pipe can prepare according to step S11 in such as Examples below 1.
In the various embodiments described above, this Nano-meter SiO_2 2the diameter of hollow pipe is 20-50nm, length 50-300nm.If adopted as step S21 in embodiment 2 prepares, the ratio regulation and control Nano-meter SiO_2 of paratartaric acid, ethanol, water, tetraethyl orthosilicate can be passed through 2the diameter of hollow pipe, length parameter etc.
In the various embodiments described above, at Nano-meter SiO_2 2surface-functionalized process method in solvent used and the Nano-meter SiO_2 of surface through functionalization 2carrying out solvent used in mixed processing process with organic carbon source can be identical or different, in one embodiment, this solvent can select the one in nitrogen dimethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), dimethylacetylamide (DMAC).
In this step S01, this is by the Nano-meter SiO_2 of surface through functionalization 2after carrying out hybrid reaction with organic carbon source, need the solvent in removing system, method except desolventizing can directly be carried out heat treated and be made solvent evaporates, in one embodiment, mixture after mixed processing is heat-treated by these at 140 DEG C, make solvent evaporate to dryness, obtain carbon source coated Si O 2composite material.
In above-mentioned steps S02, in order to make organic carbon source stable in follow-up charing processing procedure, be coated on the surface of Si material uniformly, first to the pre-oxidation treatment of composite material, in one embodiment, the method that step heats up is first heating rate 1-5 DEG C/min, after temperature is raised to 200-300 DEG C, and constant temperature 2-12 hour.In one embodiment, the method that this step heats up is first heating rate 2 DEG C/min, after temperature is raised to 250 DEG C, and constant temperature 2 hours.
In one embodiment, after pre-oxidation treatment, adopt the mode of nature cooling to the carbon source coated Si O after heat treatment 2composite material carry out annealing cooling processing.In order to prevent carbon source coated Si O 2composite material there is sintering in pre-oxidation treatment and cause the increase of particle diameter, in one embodiment, to cooled carbon source coated Si O 2composite material carry out pulverization process, as ground process.
In above-mentioned steps S03, carbonization and SiO in position 2magnesiothermic reduction reaction in, the Nano-meter SiO_2 be wrapped by 2react, by Nano-meter SiO_2 with magnesium metal generation magnesium thermal redox 2be reduced into nano Si simple substance, in the process, this nano Si simple substance is relatively by Nano-meter SiO_2 2, volume there occurs contraction, thus forms space in carbon housing, and just the expansion existing for silicon materials in these spaces provides effective space, ensures embodiment of the present invention silicon/carbon compound cathode materials structural stability in lithium ion deintercalation process.It should be understood that this magnesium should be magnesium simple substance, as magnesium powder.
While above-mentioned magnesium thermal redox reaction, be coated on Nano-meter SiO_2 2core surface be pre-oxidized process after carbon source be carbonized, production in-situ carbon, thus form in-situ carbon housing.Like this, after step S03 reaction treatment, this Nano-meter SiO_2 2be reduced into nano Si simple substance, carbon source is become in-situ carbon by final carbonization, thus forms the core-shell material of the coated nano Si simple substance nucleome of in-situ carbon housing, and is formed with space between nano Si simple substance nucleome and in-situ carbon housing.
For making magnesium powder and the SiO being coated with carbon matrix precursor 2material Homogeneous phase mixing save the heating-up time more in temperature-rise period, in one embodiment, this in-situ carburization and SiO 2magnesiothermic reduction reaction temperature be adopt to be warming up to 600-800 DEG C as the next stage:
Should with the ramp of 5-10 DEG C/min before 300 DEG C, 300 DEG C adopt the ramp of 1-5 DEG C/min to 650-800 DEG C later.
In a particular embodiment, this in-situ carburization and SiO 2magnesiothermic reduction reaction temperature be adopt to be warming up to 650-800 DEG C as the next stage:
With the ramp of 5 DEG C/min before 300 DEG C, 300 DEG C adopt the ramp of 2 DEG C/min to 650-800 DEG C later.
On the basis of the various embodiments described above, in one embodiment, this in-situ carburization and SiO 2magnesiothermic reduction reaction temperature be stabilized in 650 DEG C.
In one embodiment, the described organic carbon source coated Si O after this pre-oxidation treatment 2composite material and the mixed proportion of magnesium metal be 1:(1-2).
Effectively be carbonized and Nano-meter SiO_2 to make carbon 2be effectively reduced, and effectively improve the efficiency of reaction, in one embodiment, this in-situ carburization and SiO 2magnesiothermic reduction reaction be react 4-10 hour at 650 DEG C, with in specific embodiment, the reaction time controlled at 2 hours.
On the basis of the various embodiments described above, in this step S01, the reducing atmosphere of reaction system is (95-90): the argon gas of (5-10) and the mist of hydrogen, ensures that the nano silicon material of the generation of reduction can not be oxidized to SiOx in heat treatment process again.Be the argon gas of 95:5 and the mist of hydrogen at a specific embodiment reducing atmosphere.
Treat in-situ carburization and SiO 2magnesiothermic reduction reaction after, acidification is carried out to product, to remove impurity, as excessive magnesium, realizes the purifying of product and silicon/carbon compound cathode materials.
From the above, upper silicon/carbon compound cathode materials preparation method is by Nano-meter SiO_2 2surface-functionalized process, effectively can be combined in its surface and form nucleocapsid clad structure, make Nano-meter SiO_2 by magnesiothermic reduction reaction by carbon source 2be reduced into nano-silicon, volume shrinks in the process, thus forms certain space in carbon shell, and these spaces can provide effective space for the expansion of silicon materials, ensures material structural stability in lithium ion deintercalation process.The carbon shell that in-situ carburization is formed has good conductivity, improves cyclical stability and the high rate performance of silicon/carbon compound cathode materials further.In the method, effectively can pass through Controlling Technology parameter, the amount added as organic carbon source and magnesiothermic reduction response parameter etc., effective realization control effectively to the thickness etc. of embodiment of the present invention silicon/carbon compound cathode materials as particle size, in-situ carbon housing, thus effectively provides Stability Analysis of Structures performance and the high rate performance of silicon/carbon compound cathode materials.As in one embodiment, by the control to above-mentioned silicon/carbon compound cathode materials preparation method technological parameter, by the size controlling of product silicon/carbon compound cathode materials at 60-350nm.
In addition, above-mentioned silicon/carbon compound cathode materials preparation method uses the prices of raw and semifnished materials cheap and non-toxic, safety and environmental protection, and process conditions are to control, and prepare silicon/carbon compound cathode materials yields high, are suitable for industrial production, effectively reduce production cost.
In addition, the embodiment of the present invention additionally provides a kind of silicon/carbon compound cathode materials, and it is is core with silicon nanoparticle, take in-situ carbon as the nucleocapsid clad structure of shell, and has space between described silicon nanoparticle and described in-situ carbon housing.
In one embodiment, the size controlling of this silicon/carbon compound cathode materials is at 60-350nm.
Wherein, in another embodiment, this nano-silicon nucleome can be nano silicon spheres, also can be nano-silicon hollow pipe.When for nano silicon spheres, the diameter of this nano silicon spheres is 50-300nm.When for nano-silicon hollow pipe, this Nano-meter SiO_2 2the diameter of hollow pipe is 20-50nm, length 50-300nm.
In another embodiment, the weight of this in-situ carbon shell housing is the 10-60wt% of silicon/carbon compound cathode materials particle.
By the above-mentioned control to silicon nucleome and in-situ carbon housing parameter, realize structural stability and the electric conductivity of embodiment of the present invention silicon/carbon compound cathode materials excellence, realize cyclical stability and the high rate performance of its excellence.
Above-mentioned silicon/carbon compound cathode materials can silicon/carbon compound cathode materials preparation method by mentioned earlier prepare, and also can be prepared by additive method.When adopting silicon/carbon compound cathode materials preparation method mentioned above to prepare, the relevant parameter of this silicon/carbon compound cathode materials carries out control realization by the corresponding process parameters of silicon mentioned above/carbon compound cathode materials preparation method.
Therefore, above-mentioned silicon/carbon compound cathode materials adopts nano-silicon as nucleome, adopts in-situ carbon as housing, makes silicon/carbon compound cathode materials on the basis with high lithium storage content, have excellent electric conductivity by carbon clad structure.By the space existed between nano-silicon nucleome and carbon housing, for nano-silicon volumetric expansion retains cushion space in removal lithium embedded process, thus effectively ensure that the Stability Analysis of Structures performance of silicon/carbon compound cathode materials.
On the basis of silicon/carbon compound cathode materials described above and preparation method thereof, correspondingly, the embodiment of the present invention further provides a kind of lithium ion battery negative.Lithium ion battery negative comprises collector and is combined in the active layer containing negative material on this collector, and wherein, this negative material is silicon/carbon compound cathode materials mentioned above; The collector that collector can select this area conventional, as aluminium foil etc.Like this, this lithium ion battery negative due to containing above-mentioned silicon/carbon compound cathode materials, again because this silicon/carbon compound cathode materials has the high and good conductivity of structural stability as above, therefore, in the course of the work, this lithium ion battery negative electrode structure stability, lithium storage content is high.
At silicon/carbon compound cathode materials described above and preparation method thereof with on the basis of lithium ion battery negative, correspondingly, the embodiment of the present invention further provides a kind of lithium ion battery, and this lithium ion battery comprises lithium ion battery negative mentioned above.It is axiomatic that this lithium ion battery also comprises the necessary miscellaneous part of lithium ion battery, because this miscellaneous part is conventional, therefore, miscellaneous part is not repeated at this.
Like this, this lithium ion battery is due to containing above-mentioned lithium ion battery negative, then this lithium ion battery follows in discharge and recharge and recycles in process for a long time and has good cycle performance and high rate performance.Therefore, this lithium ion battery can such as but be not only apply in communication equipment.
The aspects such as above-mentioned silicon/carbon compound cathode materials and preparation method thereof, lithium ion battery negative and lithium ion battery are illustrated below by way of multiple embodiment.
Embodiment 1
A kind of above-mentioned silicon/carbon compound cathode materials and preparation method thereof.This silicon/carbon compound cathode materials is prepared by following method:
S11.SiO 2the preparation of nano material:
The method of sol-gel is adopted to prepare SiO 2ball, concrete grammar is as follows:
140mL ethanol mixes with 20mL water, after the ammoniacal liquor adding 3.14mL mixes, slowly drips 3mL tetraethyl orthosilicate, after stirring 3h, filters, washing, after drying, can obtain the uniform SiO of diameter at about 180nm 2microballoon.By changing the ratio of ethanol, water, ammoniacal liquor, tetraethyl orthosilicate, regulation and control SiO 2the size of microballoon, makes microballoon change between 50nm-300nm.
S12. the Surface coating of macromolecular material:
0.3gSiO prepared by step S11 2nano material ultrasonic disperse is in nitrogen dimethylformamide (DMF), add 100 microlitre aminopropyl triethoxysilanes (APTES), stir after 0.5 hour, add 0.3g polyacrylonitrile (PAN), stir 0.5 hour at 80 DEG C, at 140 DEG C, by DMF solution evaporate to dryness, and obtain the coated SiO of PAN 2material.
S13. pre-oxidation:
By SiO 2/ PAN material is positioned in Muffle furnace, and in air atmosphere, adopt the method that step heats up, heating rate 2 DEG C/min, after temperature is raised to 250 DEG C, constant temperature, after 2 hours, naturally cools to room temperature, grinds for subsequent use.
S14. in-situ carburization/magnesiothermic reduction:
The PAN/SiO of 0.2g pre-oxidation 2material is loaded in crucible, and is positioned in tube furnace after fully mixing with 0.2g magnesium powder.After vacuumizing, pass into the reducing gas of 95% argon gas/5% hydrogen, and heat up to body of heater, with the heating rate of 5 DEG C/min before 300 DEG C, 300 DEG C adopt the heating rate of 2 DEG C/min to be warming up to later
650 DEG C, and constant temperature 2 hours.Naturally cool to room temperature under reducing atmosphere, take out.By regulating pre-oxidation PAN/SiO 2with the ratio of magnesium powder, SiO can be regulated 2reducing degree.
S15. pickling:
By the dispersion of materials after obtained in-situ carburization/reduction in the hydrochloric acid solution of 2M, after stirring 5-10 hour, namely filtration, washing, drying can obtain clean, have the silicon/carbon composite of nucleocapsid structure.
Embodiment 2
A kind of above-mentioned silicon/carbon compound cathode materials and preparation method thereof.This silicon/carbon compound cathode materials has following method to prepare:
S21.SiO 2the preparation of nano material:
The method of sol-gel is adopted to prepare SiO 2hollow tube, concrete grammar is as follows:
0.1g tartaric acid is dissolved in 20mL ethanol, add 1mL water afterwards, keep solution temperature at 0 DEG C, slowly add ammoniacal liquor, regulate PH to 11, stir after 15 minutes, drip 2g tetraethyl orthosilicate, stir 2 hours at 0 DEG C, after be heated to 110 DEG C, after stirring 24, after filtration, washing, oven dry, SiO can be obtained 2hollow pipe material.
S22. the Surface coating of macromolecular material:
0.3gSiO prepared by step S21 2nano material ultrasonic disperse is in nitrogen dimethylformamide (DMF), add 100 microlitre aminopropyl triethoxysilanes (APTES), stir after 4 hours, add 0.3g polyacrylonitrile (PAN), stir 5 hours at 80 DEG C, at 140 DEG C, by DMF solution evaporate to dryness, and obtain the coated SiO of PAN 2material.
S23. pre-oxidation:
By SiO 2/ PAN material is positioned in Muffle furnace, and in air atmosphere, adopt the method that step heats up, heating rate 2 DEG C/min, after temperature is raised to 250 DEG C, constant temperature, after 2 hours, naturally cools to room temperature, grinds for subsequent use.
S24. in-situ carburization/magnesiothermic reduction:
The PAN/SiO of 0.2g pre-oxidation 2material is loaded in crucible, and is positioned in tube furnace after fully mixing with 0.2g magnesium powder.After vacuumizing, pass into the reducing gas of 95% argon gas/5% hydrogen, and heat up to body of heater, with the heating rate of 5 DEG C/min before 300 DEG C, 300 DEG C adopt the heating rates of 2 DEG C/min to be warming up to 700 DEG C later, and constant temperature 6 hours.Naturally cool to room temperature under reducing atmosphere, take out.By regulating pre-oxidation PAN/SiO 2with the ratio of magnesium powder, SiO can be regulated 2reducing degree.
S25. pickling:
By the dispersion of materials after obtained in-situ carburization/reduction in the hydrochloric acid solution of 2M, after stirring 5-10 hour, namely filtration, washing, drying can obtain clean, have the silicon/carbon composite of nucleocapsid structure.
Embodiment 3
A kind of above-mentioned silicon/carbon compound cathode materials and preparation method thereof.This silicon/carbon compound cathode materials has following method to prepare:
S31.SiO 2the preparation of nano material:
The method of sol-gel is adopted to prepare SiO 2ball, concrete grammar is as follows:
140mL ethanol mixes with 30mL water, after the ammoniacal liquor adding 6.5mL mixes, slowly drips 3mL tetraethyl orthosilicate, after stirring 3h, filters, washing, after drying, can obtain the uniform SiO of diameter at about 100nm 2microballoon.
S32. the Surface coating of macromolecular material:
0.4gSiO prepared by step S11 2nano material ultrasonic disperse, in DMSO, adds 120 microlitre aminopropyl triethoxysilanes (APTES), stirs after 1 hour, add 0.6g polyacrylonitrile (PAN), stir 2 hours at 80 DEG C, at 140 DEG C, by DMSO solution evaporate to dryness, and obtain the coated SiO of PAN 2material.
S33. pre-oxidation:
By SiO 2/ PAN material is positioned in Muffle furnace, and in air atmosphere, adopt the method that step heats up, heating rate 1 DEG C/min, after temperature is raised to 250 DEG C, constant temperature, after 4 hours, naturally cools to room temperature, grinds for subsequent use.
S34. in-situ carburization/magnesiothermic reduction:
The PAN/SiO of 0.3g pre-oxidation 2material is loaded in crucible, and is positioned in tube furnace after fully mixing with 0.35g magnesium powder.After vacuumizing, pass into the reducing gas of 90% argon gas/10% hydrogen, and heat up to body of heater, with the heating rate of 10 DEG C/min before 300 DEG C, 300 DEG C adopt the heating rates of 3 DEG C/min to be warming up to 800 DEG C later, and constant temperature 5 hours.Naturally cool to room temperature under reducing atmosphere, take out.By regulating pre-oxidation PAN/SiO 2with the ratio of magnesium powder, SiO can be regulated 2reducing degree.
S35. pickling:
By the dispersion of materials after obtained in-situ carburization/reduction in the hydrochloric acid solution of 1.5M, stir after 12 hours, namely filtration, washing, drying can obtain clean, have the silicon/carbon composite of nucleocapsid structure.
Embodiment 4
S41.SiO 2the preparation of nano material:
The method of sol-gel is adopted to prepare SiO 2hollow tube, concrete grammar is as follows:
0.2g tartaric acid is dissolved in 30mL ethanol, add 1.5mL water afterwards, keep solution temperature at 0 DEG C, slowly add ammoniacal liquor, regulate PH to 11, stir after 20 minutes, drip 2.5g tetraethyl orthosilicate, stir 3 hours at 0 DEG C, after be heated to 110 DEG C, after stirring 24, after filtration, washing, oven dry, SiO can be obtained 2hollow pipe material.
S42. the Surface coating of macromolecular material:
0.2gSiO prepared by step S41 2nano material ultrasonic disperse, in DMAC, adds 80 microlitre aminopropyl triethoxysilanes (APTES), stirs after 5 hours, add 0.3g polyacrylonitrile (PAN), stir 4 hours at 80 DEG C, at 120 DEG C, by DMF solution evaporate to dryness, and obtain the coated SiO of PAN 2material.
S43. pre-oxidation:
By SiO 2/ PAN material is positioned in Muffle furnace, and in air atmosphere, adopt the method that step heats up, heating rate 2 DEG C/min, after temperature is raised to 250 DEG C, constant temperature, after 3 hours, naturally cools to room temperature, grinds for subsequent use.
S44. in-situ carburization/magnesiothermic reduction:
The PAN/SiO of 0.2g pre-oxidation 2material is loaded in crucible, and is positioned in tube furnace after fully mixing with 0.3g magnesium powder.After vacuumizing, pass into the reducing gas of 95% argon gas/5% hydrogen, and heat up to body of heater, with the heating rate of 8 DEG C/min before 300 DEG C, 300 DEG C adopt the heating rates of 4 DEG C/min to be warming up to 650 DEG C later, and constant temperature 8 hours.Naturally cool to room temperature under reducing atmosphere, take out.By regulating pre-oxidation PAN/SiO 2with the ratio of magnesium powder, SiO can be regulated 2reducing degree.
S45. pickling:
By the dispersion of materials after obtained in-situ carburization/reduction in the hydrochloric acid solution of 1M, stir after 15 hours, namely filtration, washing, drying can obtain clean, have the silicon/carbon composite of nucleocapsid structure.
Lithium ion battery embodiment
Silicon/the carbon composite provided in the various embodiments described above lithium ion battery negative preparation method is conveniently prepared into lithium ion battery negative respectively.
According to lithium ion battery customary preparation methods, the lithium ion battery negative utilizing the silicon/carbon composite provided in the various embodiments described above to prepare is assembled into lithium ion battery respectively.
Comparative example 1
Directly utilize nano-silicon for negative material, respectively nano-silicon negative material is prepared lithium ion battery negative and lithium ion battery according to the method in lithium ion battery embodiment.
Performance test:
1. silicon/carbon composite that prepared by couple above-described embodiment 1-4 carries out micro-analysis:
Silicon/the carbon composite prepared by above-described embodiment 1 carries out ESEM and projection electronic microscope photos.
Wherein, the scanning electron microscope analysis of silicon/carbon composite prepared by embodiment 1 is as described in Fig. 2 a, and projection electronic microscope photos is as described in Fig. 2 b.From the picture of Fig. 2 a, 2b, this silicon/carbon compound cathode materials is that nanometer is spherical, and its diameter is about 200nm, and its particle diameter respectively evenly.Learn by analyzing further, the nano-silicon diameter in this silicon/carbon compound cathode materials is about 180nm, and the thickness of original position carbon-coating is 10-20nm.
Silicon/carbon compound cathode materials prepared by embodiment 2 is nanotube-shaped, and its diameter is 20-30nm, length 200-300nm.Equally, this nanotube-shaped silicon/carbon compound cathode materials size uniform.Learn by analyzing further, the thickness of this silicon/carbon compound cathode materials situ carbon-coating is 15-20nm.
Through analyzing the silicon/carbon compound cathode materials prepared in embodiment 2-4, close in the ESEM of the silicon/carbon compound cathode materials prepared in those embodiments and projection electronic microscope photos result and embodiment 1.
2. be that the lithium ion battery prepared for the various embodiments described above and comparative example carries out cycle performance and high rate performance test below, this cycle performance and high rate performance method of testing are conventionally carried out, and record result as follows:
As shown in Figure 3, high rate performance test result as shown in Figure 4 for embodiment 1 and the cycle performance of lithium ion battery test result in comparative example 1.From Fig. 3,4, in embodiment 1, the cycle performance of lithium ion battery is apparently higher than the lithium ion battery in comparative example 1.And its high rate performance is excellent.
By test, the cycle performance of the lithium ion battery in embodiment 2-4 is similar to embodiment 1 with high rate performance, all apparently higher than lithium ion battery in comparative example 1.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. silicon/carbon compound cathode materials preparation method, comprises the steps:
In a solvent, by the Nano-meter SiO_2 of surface through functionalization 2mix with organic carbon source, make described organic carbon source be coated on described Nano-meter SiO_2 2surface, after desolventizing, obtains organic carbon source coated Si O 2composite material;
By described organic carbon source coated Si O 2composite material adopt step heat up method carry out pre-oxidation treatment;
In reducing atmosphere, by the described organic carbon source coated Si O after described pre-oxidation treatment 2composite material and magnesium at 600-800 DEG C, carry out in-situ carburization and SiO 2magnesiothermic reduction reaction, after question response terminates, carry out pickling.
2. silicon according to claim 1/carbon compound cathode materials preparation method, it is characterized in that: the method that the method that described employing step heats up carries out pre-oxidation treatment is: first heating rate 1-5 DEG C/min, after temperature is raised to 200-300 DEG C, constant temperature 2-12 hour.
3. silicon according to claim 1/carbon compound cathode materials preparation method, is characterized in that: described in-situ carburization and SiO 2magnesiothermic reduction reaction temperature be adopt to be warming up to 600-800 DEG C as the next stage:
With the ramp of 1-10 DEG C/min before 300 DEG C, 300 DEG C adopt the ramp of 2-10 DEG C/min to 600-800 DEG C later.
4., according to the arbitrary described silicon/carbon compound cathode materials preparation method of claim 1-3, it is characterized in that: described surface is through the Nano-meter SiO_2 of functionalization 2with organic carbon source mass ratio 1:(1-5); And/or
Described organic carbon source selects the mixture of any one or more in polyacrylonitrile, polyvinyl alcohol, polypyrrole.
5., according to the arbitrary described silicon/carbon compound cathode materials preparation method of claim 1-3, it is characterized in that: described Nano-meter SiO_2 2select Nano-meter SiO_2 2ball or Nano-meter SiO_2 2one or both mixture in hollow pipe; And/or
Described Nano-meter SiO_2 2the diameter of ball be 50nm-300nm it; Described Nano-meter SiO_2 2the diameter of hollow pipe is 20-50nm, length 50-300nm.
6., according to the arbitrary described silicon/carbon compound cathode materials preparation method of claim 1-3, it is characterized in that: described Nano-meter SiO_2 2the method of surface-functionalized process as follows:
In a solvent, by described Nano-meter SiO_2 2with silane coupler according to mass ratio 100:(1-5) ratio carry out mixed processing 2-10 hour.
7. silicon/carbon compound cathode materials, it is is core with silicon nanoparticle, take in-situ carbon as the nucleocapsid clad structure of shell, and has space between described silicon nanoparticle and described in-situ carbon housing.
8. silicon according to claim 7/carbon compound cathode materials preparation method, is characterized in that: described silicon nanoparticle is nano silicon spheres or nano-silicon hollow pipe; Wherein, the diameter of described nano silicon spheres is 50-300nm, described Nano-meter SiO_2 2the diameter of hollow pipe is 20-50nm, length 50-300nm; And/or
The weight of described in-situ carbon housing is 20-60wt%.
9. a lithium ion battery negative, comprise collector and be combined on described collector containing the active layer of negative material, it is characterized in that: described negative material is silicon/carbon compound cathode materials of preparing of described silicon/carbon compound cathode materials preparation method as arbitrary in claim 1 ~ 6 or silicon/carbon compound cathode materials as claimed in claim 7.
10. a lithium ion battery, is characterized in that, described lithium ion battery comprises lithium ion battery negative according to claim 9.
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