CN106711415B - A kind of porous silicon composite cathode material and preparation method thereof - Google Patents

A kind of porous silicon composite cathode material and preparation method thereof Download PDF

Info

Publication number
CN106711415B
CN106711415B CN201611177897.0A CN201611177897A CN106711415B CN 106711415 B CN106711415 B CN 106711415B CN 201611177897 A CN201611177897 A CN 201611177897A CN 106711415 B CN106711415 B CN 106711415B
Authority
CN
China
Prior art keywords
porous silicon
presoma
conductive
silicon
cladding
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611177897.0A
Other languages
Chinese (zh)
Other versions
CN106711415A (en
Inventor
陈溢镭
何畅雷
夏永高
刘兆平
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Fuli Battery Material Technology Co Ltd
Original Assignee
Ningbo Fuli Battery Material Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Fuli Battery Material Technology Co Ltd filed Critical Ningbo Fuli Battery Material Technology Co Ltd
Priority to CN201611177897.0A priority Critical patent/CN106711415B/en
Publication of CN106711415A publication Critical patent/CN106711415A/en
Application granted granted Critical
Publication of CN106711415B publication Critical patent/CN106711415B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Silicon Compounds (AREA)

Abstract

The present invention provides a kind of porous silicon composite cathode material, including porous silicon matrix, it is compounded in the first conductive material layer of the porous silicon matrix surface, and is compounded in the nano silica-base material of the first conductive material layer surface.The present invention uses conductive material to carry out first time cladding first, then continue composite Nano silica-base material in conductive material layer surface again, obtain porous silicon composite cathode material, the higher first charge-discharge efficiency that porous silica material itself has not only is utilized, and the conductive material for being coated on porous silica material surface can not only increase the electric conductivity of composite material, porous silica material can also be inhibited, which to expand outward, to be caused to rupture, and improves cyclical stability；Surface after composite Nano silica-base material, has better cycle performance, the cycle performance of porous silica material composite material can be improved again；In addition, preparation method of the invention is easy to operate, safe, versatile, production cost is low, is suitble to industrialized production.

Description

A kind of porous silicon composite cathode material and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion battery electrode, it is related to a kind of porous silicon composite cathode material and its system Preparation Method more particularly to a kind of porous silicon composite cathode material and preparation method thereof for lithium ion battery.
Background technique
Lithium ion battery is high with operating voltage, specific energy is high, have extended cycle life, is light-weight, self discharge is few, memoryless effect It should be with cost performance ratio, it has also become the fields such as high power electric vehicle, artificial satellite, aerospace rechargeable type power supply Main selecting object.Especially in practical applications, lithium ion battery has become the ideal of all kinds of portable electronic devices The energy, such as laptop, mobile phone etc..However current lithium ion battery can no longer meet fast-developing electric car The requirement of equal novel electrons equipment, needs higher energy density, cycle life and lower cost.
Therefore, lithium ion battery and its associated materials become the research hotspot of numerous manufacturers and scientific research personnel.In addition to anode Material is other than lithium ion battery critical material, and negative electrode material equally decides that the performance of lithium ion battery, graphite type material are The main negative electrode material of lithium ion electronics, theoretical specific capacity are only 372mAh/g, limit the energy density of lithium ion battery.
And the silica-base material being widely noticed at present, it is a kind of novel cathode material for lithium ion battery, there is high theoretical embedding lithium Specific capacity 4200mAh/g, and rich reserves.But violent contraction and expansion occur in charge and discharge process for silicium cathode, Volume change is more than 300%, leads to silicon particle dusting, and active material is detached from binder；Simultaneously SEI film in cyclic process not Disconnected rupture and regeneration, constantly consumption electrolyte, reduce cyclical stability.
The study found that porous silicon can effectively improve the cycle performance of battery, Mingyuan Ge etc. utilizes AgNO3And HF Electrochemical etching silicon nanowires obtains porous silicon nanowires.(Porous Doped Silicon Nanowires for Lithium Ion Battery Anode with Long Cycle Life, Nano Lett, 2012,12,2318-2323). The porous silicon prepared in this way can reach better cycle performance and first discharge specific capacity, but its preparation cost really Height, operation difficulty is big, increases production requirement and difficulty, therefore it is only limitted to small lot preparation at present, can not be pushed away on a large scale Extensively.Jiang Zhiyu et al. is prepared for the porous silicons of different porosities using acid corrosion silicon alloy, and (Jiang Zhiyu, a kind of lithium ion battery are more Hole silicium cathode material and its preparation method and application: China, 103165874A [P], 2013-06-19), although this porous silicon It can commercially produce, there is high cycle efficieny for the first time, but its porous structure is easily destroyed, and causes it in charge and discharge process Active material is detached from, and shortens cycle life.
Therefore, how to obtain that a kind of preparation method is simple, and there can be the porous silicium cathode material of preferable electrical property Material is always all multi-vendor and researcher's extensive concern in the complex art problem and field of field of lithium ion battery Problem.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of porous silicon composite cathode material and its preparation Method, especially a kind of porous silicon composite cathode material and preparation method thereof for lithium ion battery are provided by the invention more Hole silicon composite cathode material, discharging efficiency for the first time with higher and preferable cyclical stability, and system provided by the invention Preparation Method is easy to operate, it is safe, versatile, be suitable for large-scale production and application.
The present invention provides a kind of porous silicon composite cathode material, including porous silicon matrix, it is compounded in the porous silicon-base First conductive material layer in body surface face, and it is compounded in the nano silica-base material of the first conductive material layer surface.
It preferably, further include the second outer layer of conductive material for being compounded in the nano silica-base material surface.
Preferably, the porous silicon matrix is porous silicon particle；
The nano silica-base material include the mixture of silicon nanoparticle and nanometer conductive material, the oxygen-containing silicon particle of nanometer and One of mixture and silicon nanoparticle of nanometer conductive material are a variety of；
The mass ratio of the nano silica-base material and the porous silicon matrix is (1~2): (3~12).
Preferably, first conductive material include conductive carbon material, conductive carbon material and alloy material mixture or Alloy material；
The mass ratio of first conductive material and the porous silicon matrix is 1:(3~12)；
Second conductive material includes the mixture or alloy material of conductive carbon material, conductive carbon material and alloy material Material；The mass ratio of second conductive material and the porous silicon matrix is 1:(3~12)；
The alloy material includes metallic element alloy and/or metallic element and nonmetalloid alloy.
Preferably, the conductive carbon material includes graphene, carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, receives Meter Shi Mo, cracking one of carbon and conductive black or a variety of.
The present invention also provides a kind of preparation methods of porous silicon composite cathode material, comprising the following steps:
(1) porous silicon matrix is coated using the first conductive material presoma, then handles 5 at 400~1600 DEG C ~10 hours, obtain the first presoma；
The first conductive material presoma includes conductive carbon material material precursor, conductive carbon material material precursor and alloy material The mixture or alloy material presoma of presoma；
The cladding includes emulsification cladding, liquid phase coating, gas phase cladding or solid phase cladding；
(2) the first presoma and the progress of nano silicon-based raw material is compound, then handled 5~10 hours at 400~1600 DEG C, Obtain porous silicon composite cathode material；
The nano silicon-based raw material includes the mixture of silicon source or silicon source and other raw materials；Other described raw materials include receiving Rice conductive material and/or conductive carbon material material precursor；
It is described compound including emulsification is compound, liquid phase is compound, gaseous recombination or solid phase are compound.
Preferably, cladding processing is carried out again to the porous silicon composite cathode material；
The cladding processing are as follows: porous silicon composite cathode material is coated using the second conductive material presoma, so It is handled 5~10 hours at 400~1500 DEG C afterwards；
The second conductive material presoma includes conductive carbon material material precursor, conductive carbon material material precursor and alloy material The mixture or alloy material presoma of presoma；
The cladding includes emulsification cladding, liquid phase coating, gas phase cladding or solid phase cladding；
The mass ratio of the porous silicon composite cathode material and the second conductive presoma is (5~10): 1.
Preferably, the conductive carbon material material precursor includes sucrose, glucose, phenolic resin and melamino-formaldehyde, first One of alkane and ethylene are a variety of；
The alloy material presoma includes molysite, aluminium salt, pink salt, mantoquita, titanium salt, aluminum oxide, stannic oxide, two One of titanium oxide and copper oxide are a variety of；
The silicon source includes SiH4、Si2H6、Si3H8、SiCl4、SiHCl3、Si2Cl6、SiH2Cl2And SiH3One of Cl Or it is a variety of.
Preferably, cladding in the step (1) specifically:
Porous silicon and the first conductive material presoma are dispersed with stirring or are dissolved in a solvent, is then spray-dried, obtains Coat product；
The mass ratio of the porous silicon and the first conductive presoma is (1~2): (1~5)；The solvent be water, ethyl alcohol, One of formaldehyde and toluene are a variety of；
Or are as follows:
By porous silicon and the first conductive material presoma mixing and ball milling 5~for 24 hours, cladding product is obtained；The porous silicon with The mass ratio of first conductive presoma is (1~2): (1~5)；
Or are as follows:
Porous silicon is passed through to inert gas and the first conductive material presoma at 500~1500 DEG C, then natural cooling To room temperature, cladding product is obtained；The mass ratio of the porous silicon and the first conductive presoma is (1~2): (1~5)；Indifferent gas Body includes nitrogen and/or argon gas；
Or are as follows:
By porous silicon and the first conductive presoma mixing and ball milling 5~for 24 hours, indifferent gas then is passed through at 500~1500 DEG C 5~20h of body and reducibility gas, cooled to room temperature obtain cladding product；The porous silicon and the first conductive presoma Mass ratio is (1~2): (1~5)；The inert gas includes nitrogen and/or argon gas；The reducibility gas include hydrogen and/ Or ammonia；
Or are as follows:
It disperses porous silicon and the first conductive presoma in the solvent containing emulsifier, stir 5 at 10~100 DEG C~ 20h is then centrifuged for obtaining cladding product；The mass ratio of the porous silicon and the first conductive presoma is (1~2): (1~5)；Institute Stating emulsifier includes one of Triton X-100, Span series and twain series emulsifier or a variety of.
It is preferably, compound in the step (2) specifically:
First presoma and nano silicon-based raw material are dispersed with stirring in a solvent, are then spray-dried, combination product is obtained； The mass ratio of first presoma and nano silicon-based raw material is (1~2): (1~5)；The solvent be water, ethyl alcohol, formaldehyde and One of toluene is a variety of；
Or are as follows:
By the first presoma and nano silicon-based raw material mixing and ball milling 5~for 24 hours, combination product is obtained；First presoma Mass ratio with nano silicon-based raw material is (1~2): (1~5)；
Or are as follows:
First presoma is passed through inert gas and nano silicon-based raw material at 500~1500 DEG C, is then naturally cooled to Room temperature obtains combination product；The mass ratio of first presoma and nano silicon-based raw material is (1~2): (1~5)；It is described lazy Property gas includes nitrogen and/or argon gas；
Or are as follows:
By the first presoma and nano silicon-based stock dispersion in the solvent containing emulsifier, 5 are stirred at 10~100 DEG C ~20h is then centrifuged for obtaining combination product；The mass ratio of first presoma and nano silicon-based raw material is (1~2): (1~ 5)；The emulsifier includes one of Triton X-100, Span series and twain series emulsifier or a variety of.
The present invention provides a kind of porous silicon composite cathode material, including porous silicon matrix, it is compounded in the porous silicon-base First conductive material layer in body surface face, and it is compounded in the nano silica-base material of the first conductive material layer surface.With it is existing Technology is compared, and for silicium cathode violent contraction and expansion occur in charge and discharge process for the present invention, leads to silicon particle dusting, living Property substance be detached from binder；The constantly rupture and regeneration in cyclic process of SEI film, constantly consumption electrolyte simultaneously, reduce and follow Many defects such as ring stability.The present invention uses conductive material to carry out first time cladding first, then again in conductive material layer Composite Nano silica-base material is continued on surface, obtains porous silicon composite cathode material, porous silica material itself, which is not only utilized, to be had Higher first charge-discharge efficiency, and the conductive material for being coated on porous silica material surface can not only increase composite material Electric conductivity, porous silica material can also be inhibited, which to expand outward, to be caused to rupture, and improves cyclical stability；Surface composite Nano silicon again After sill, there is better cycle performance, the cycle performance of porous silica material composite material can be improved；In addition, of the invention Preparation method it is easy to operate, safe, versatile, production cost is low, be suitble to industrialized production.The experimental results showed that this hair Bright porous silicon composite cathode material has height ratio capacity (> 1300mAh/g), high first charge-discharge efficiency (> 85%) and Gao Xun Ring performance (150 circulations, capacity retention ratio are 90% or more).
Detailed description of the invention
Fig. 1 is porous silicon-base composite negative pole material SEM figure prepared by the embodiment of the present invention 7；
Fig. 2 is the first charge-discharge cyclic curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 7；
Fig. 3 is the cycle performance curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 7；
Fig. 4 is the efficiency for charge-discharge curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 7；
Fig. 5 is the cycle performance curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 9；
Fig. 6 is the efficiency for charge-discharge curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 9.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or lithium ion battery The purity of field routine.
The present invention provides a kind of porous silicon composite cathode material, including porous silicon matrix, it is compounded in the porous silicon-base First conductive material layer in body surface face, and it is compounded in the nano silica-base material of the first conductive material layer surface.
The porous silicon matrix is not particularly limited in the present invention, with porous silica material well known to those skilled in the art or It is used to prepare the porous silica material of negative electrode material, those skilled in the art can be according to practical situations, quality requirement And properties of product are selected and are adjusted, porous silicon matrix of the present invention is preferably porous silicon particle；It is of the present invention more The average particle size of hole silicon substrate is preferably 0.1~30 μm, more preferably 0.5~25 μm, more preferably 1~20 μm, most preferably 5 ~15 μm.The maximum particle size of porous silicon matrix of the present invention is preferably smaller than equal to 40 μm, more preferably less than or equal to 35 μm, optimal Choosing is less than or equal to 30 μm.The magnetisable material content of porous silicon matrix of the present invention is preferably smaller than equal to 50ppm, more preferably less than Equal to 45ppm, most preferably less than it is equal to 40ppm.The specific surface area of porous silicon matrix of the present invention is preferably 30~ 600cm2/ g, more preferably 100~500cm2/ g, most preferably 200~400cm2/g。
First conductive material is not particularly limited in the present invention, with conductive material well known to those skilled in the art or It is usually used in the conductive material of the cathode of lithium ion battery, those skilled in the art can be according to practical situations, quality It is required that and properties of product selected and adjusted, the first conductive material of the present invention preferably includes conductive carbon material, or leads The mixture of the mixture of electrical carbon material and alloy material, more preferably conductive carbon material and alloy material.
First conductive carbon material is not particularly limited in the present invention, with conductive carbon material well known to those skilled in the art Expect or be usually used in lithium ion battery cathode conductive carbon material, those skilled in the art can be according to practical application feelings Condition, quality requirement and properties of product are selected and are adjusted, the first conductive carbon material of the present invention preferably include graphene, Carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, nano-graphite, cracking one of carbon and conductive black or a variety of, more Preferably graphene, carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, nano-graphite, cracking carbon or conductive black.This hair It is bright that the alloy material is not particularly limited, with alloy material well known to those skilled in the art or it is usually used in lithium ion battery Cathode alloy material, those skilled in the art can be according to practical situations, quality requirement and properties of product It is selected and is adjusted, alloy material of the present invention preferably includes metallic element alloy and/or metallic element and nonmetallic member Element alloy, more preferably metallic element alloy or metallic element and nonmetalloid alloy.The present invention does not have the metallic element There is special limitation, i.e. with the metallic element of metallic element well known to those skilled in the art or the electrode for being usually used in lithium ion battery Can, those skilled in the art can select and adjust, this hair according to practical situations, quality requirement and properties of product The bright metallic element preferably includes titanium, tin, aluminium, iron, copper, antimony, nickel, manganese, cobalt, germanium, zinc, bismuth and two or more in sowing, more Preferably titanium, tin, aluminium, iron, copper, antimony, nickel, manganese, cobalt, germanium, zinc, bismuth and two or three in sowing.The present invention is to described nonmetallic Element is not particularly limited, and with nonmetalloid well known to those skilled in the art, those skilled in the art can basis Practical situations, quality requirement and properties of product are selected and are adjusted, and nonmetalloid of the present invention preferably includes Silicon and/or nitrogen, more preferably silicon or nitrogen.
The dosage of the conductive carbon material and alloy material is not particularly limited in the present invention, ripe with those skilled in the art The conventional amount used known, those skilled in the art can carry out according to practical situations, quality requirement and properties of product It selects and adjusts, in the mixture of conductive carbon material and alloy material of the present invention, the conductive carbon material and the alloy The mass ratio of the mixture of material is preferably (1~20): (20~1), more preferably (5~15): (15~5), most preferably (7 ~12): (12~7).
The dosage of first conductive material is not particularly limited in the present invention, with routine well known to those skilled in the art Dosage, those skilled in the art can select and adjust according to practical situations, quality requirement and properties of product Whole, the content that the first conductive material of the present invention accounts for the porous silicon composite cathode material is preferably 0.1wt%~50wt%, More preferably 0.5wt%~40wt%, more preferably 1wt%~30wt%, most preferably 10wt%~20wt%.The present invention couple The thickness of first conductive material layer is not particularly limited, and those skilled in the art can be according to practical situations, quality It is required that and properties of product selected and adjusted, the thickness of the first conductive material layer of the present invention is preferably 1~500nm, More preferably 10~450nm, more preferably 50~400nm, more preferably 100~300nm.
The compound definition is not particularly limited in the present invention, is with composite definitions well known to those skilled in the art Can, the present invention preferably coats, half cladding, stacking, growth, insertion, one of doping and deposition or a variety of, of the present invention The compound more preferably cladding or half being compounded in the first conductive material layer of the porous silicon matrix surface coat, most preferably Cladding.The cladding is not particularly limited in the present invention, with cladding well known to those skilled in the art definition, this field skill Art personnel can select and adjust according to practical situations, quality requirement and properties of product.
The nano silica-base material is not particularly limited in the present invention, with conductive material well known to those skilled in the art Nano silica-base material, those skilled in the art can carry out according to practical situations, quality requirement and properties of product Selection and adjustment, nano silica-base material of the present invention preferably include the mixture of silicon nanoparticle and nanometer conductive material, receive One of mixture, nano silicon film and silicon nanoparticle of the oxygen-containing silicon particle of rice and nanometer conductive material is a variety of, more preferably For mixture, the nanometer of the mixture of silicon nanoparticle and nanometer conductive material, nanometer oxygen-containing silicon particle and nanometer conductive material Silicon fiml or silicon nanoparticle.
The granularity of the silicon nanoparticle is not particularly limited in the present invention, with nano-silicon well known to those skilled in the art The granularity of particle, those skilled in the art can select according to practical situations, quality requirement and properties of product It selects and adjusts, the average particle size of silicon nanoparticle of the present invention is preferably 1.0~900nm, more preferably 10~800nm, more Preferably 100~700nm, most preferably 300~500nm.The nano silicon film is not particularly limited in the present invention, with this field Nano silicon film known to technical staff, those skilled in the art can be according to practical situations, quality requirement and productions Moral character can be carried out selection and adjustment, and nano silicon film of the present invention is preferably continuous nano silicon film；Nano-silicon of the present invention The thickness of film is preferably 1.0~900nm, more preferably 10~800nm, more preferably 100~700nm, most preferably 300~ 500nm.The oxygen-containing silicon particle of the nanometer is not particularly limited in the present invention, with the oxygen-containing silicon of nanometer well known to those skilled in the art Particle, those skilled in the art can select and adjust according to practical situations, quality requirement and properties of product Whole, the oxygen-containing silicon particle molecular formula of nanometer of the present invention is preferably SiOx, wherein the value range of x is preferably 0.3≤x≤1.5, More preferably 0.5≤x≤1.2, most preferably 0.7≤x≤1.0.The present invention does not have the granularity of the oxygen-containing silicon particle of the nanometer Especially limitation, with the granularity of the oxygen-containing silicon particle of nanometer well known to those skilled in the art, those skilled in the art can root It is selected and is adjusted according to practical situations, quality requirement and properties of product, average particle size of the present invention is preferably 1.0~900nm, more preferably 10~800nm, more preferably 100~700nm, most preferably 300~500nm.
The dosage of the nano silica-base material is not particularly limited in the present invention, with routine well known to those skilled in the art Dosage, those skilled in the art can select and adjust according to practical situations, quality requirement and properties of product Whole, the mass ratio that nano silica-base material of the present invention accounts for the porous silicon matrix is preferably (1~2): (3~12), more preferably For (1.2~1.8): (5~10), more preferably (1.3~1.7): (6~9), most preferably (1.4~1.6): (7~8).This hair It is bright that the ratio of the two is not particularly limited when being preferably silicon nanoparticle and nanometer conductive material to the nano silica-base material, With conventional amount used well known to those skilled in the art and ratio, those skilled in the art can according to practical situations, Quality requirement and properties of product are selected and are adjusted, the mixture of silicon nanoparticle and nanometer conductive material of the present invention In, the content of the nanometer conductive material is preferably 0.1wt%~50wt%, more preferably 0.5wt%~40wt%, more preferably For 1wt%~30wt%, most preferably 10wt%~20wt%.The present invention is preferably that nanometer is oxygen-containing to the nano silica-base material When silicon particle and nanometer conductive material, the additional proportion of the two is not particularly limited, with routine well known to those skilled in the art Dosage and ratio, those skilled in the art can select according to practical situations, quality requirement and properties of product It selects and adjusts, in the mixture of the oxygen-containing silicon particle of nanometer of the present invention and nanometer conductive material, the nanometer conductive material Content is preferably 0.1wt%~50wt%, more preferably 0.5wt%~40wt%, more preferably 1wt%~30wt%, optimal It is selected as 10wt%~20wt%.
The compound definition is not particularly limited in the present invention, is with composite definitions well known to those skilled in the art Can, the present invention preferably coats, half cladding, stacking, growth, insertion, one of doping and deposition or a variety of, of the present invention Compound more preferably insertion or the doping being compounded in the nano silica-base material of the first conductive material layer surface, most preferably Doping.The doping is not particularly limited in the present invention, with doping well known to those skilled in the art definition, this field skill Art personnel can select and adjust according to practical situations, quality requirement and properties of product.
The present invention is to further increase the stability and electric conductivity of porous silicon composite cathode material, and the porous silicon is compound Negative electrode material further preferably includes being compounded in second outer layer of conductive material on the nano silica-base material surface, i.e., described nano silicon-based Material surface compound second outer layer of conductive material again.
Second conductive material is not particularly limited in the present invention, with conductive material well known to those skilled in the art or It is usually used in the conductive material of the cathode of lithium ion battery, those skilled in the art can be according to practical situations, quality It is required that and properties of product selected and adjusted, the second conductive material of the present invention preferably includes conductive carbon material, or leads The mixture of the mixture of electrical carbon material and alloy material, more preferably conductive carbon material and alloy material.
Second conductive carbon material is not particularly limited in the present invention, with conductive carbon material well known to those skilled in the art Expect or be usually used in lithium ion battery cathode conductive carbon material, those skilled in the art can be according to practical application feelings Condition, quality requirement and properties of product are selected and are adjusted, the second conductive carbon material of the present invention preferably include graphene, Carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, nano-graphite, cracking one of carbon and conductive black or a variety of, more Preferably graphene, carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, nano-graphite, cracking carbon or conductive black.This hair It is bright that the alloy material is not particularly limited, with alloy material well known to those skilled in the art or it is usually used in lithium ion battery Cathode alloy material, those skilled in the art can be according to practical situations, quality requirement and properties of product It is selected and is adjusted, alloy material of the present invention preferably includes metallic element alloy and/or metallic element and nonmetallic member Element alloy, more preferably metallic element alloy or metallic element and nonmetalloid alloy.The present invention does not have the metallic element There is special limitation, i.e. with the metallic element of metallic element well known to those skilled in the art or the electrode for being usually used in lithium ion battery Can, those skilled in the art can select and adjust, this hair according to practical situations, quality requirement and properties of product The bright metallic element preferably includes titanium, tin, aluminium, iron, copper, antimony, nickel, manganese, cobalt, germanium, zinc, bismuth and two or more in sowing, more Preferably titanium, tin, aluminium, iron, copper, antimony, nickel, manganese, cobalt, germanium, zinc, bismuth and two or three in sowing.The present invention is to described nonmetallic Element is not particularly limited, and with nonmetalloid well known to those skilled in the art, those skilled in the art can basis Practical situations, quality requirement and properties of product are selected and are adjusted, and nonmetalloid of the present invention preferably includes Silicon and/or nitrogen, more preferably silicon or nitrogen.
The dosage of the conductive carbon material and alloy material is not particularly limited in the present invention, ripe with those skilled in the art The conventional amount used known, those skilled in the art can carry out according to practical situations, quality requirement and properties of product It selects and adjusts, in the mixture of conductive carbon material and alloy material of the present invention, the conductive carbon material and the alloy The mass ratio of the mixture of material is preferably (1~20): (20~1), more preferably (5~15): (15~5), most preferably (7 ~12): (12~7).
The dosage of second conductive material is not particularly limited in the present invention, with routine well known to those skilled in the art Dosage, those skilled in the art can select and adjust according to practical situations, quality requirement and properties of product Whole, the content that the second conductive material of the present invention accounts for the porous silicon composite cathode material is preferably 0.1wt%~50wt%, More preferably 0.5wt%~40wt%, more preferably 1wt%~30wt%, most preferably 10wt%~20wt%.The present invention couple The thickness of second conductive material layer is not particularly limited, and those skilled in the art can be according to practical situations, quality It is required that and properties of product selected and adjusted, the thickness of the second conductive material layer of the present invention is preferably 10~ 900nm, more preferably 100~800nm, more preferably 200~700nm, most preferably 300~600nm.In addition, the present invention couple The dosage of the conductive material, i.e. the first conductive material, the dosage of the second conductive material are not particularly limited, with art technology Conventional amount used known to personnel, those skilled in the art can be according to practical situations, quality requirement and products Can be carried out selection and adjustment, the mass ratio of the first conductive material of the present invention and the porous silicon matrix be preferably 1:(3~ 12), more preferably 1:(5~10), most preferably 1:(7~8)；Second conductive material of the present invention and the porous silicon matrix Mass ratio be preferably 1:(3~12), more preferably 1:(5~10), most preferably 1:(7~8).
The compound definition is not particularly limited in the present invention, is with composite definitions well known to those skilled in the art Can, the present invention preferably coats, half cladding, stacking, growth, insertion, one of doping and deposition or a variety of, of the present invention The compound more preferably cladding or half being compounded in the first conductive material layer of the porous silicon matrix surface coat, most preferably Cladding.The cladding is not particularly limited in the present invention, with cladding well known to those skilled in the art definition, this field skill Art personnel can select and adjust according to practical situations, quality requirement and properties of product.
Above-mentioned steps of the present invention provide a kind of porous silicon composite cathode material, and the present invention uses conductive material to carry out first It coats for the first time, then continues composite Nano silica-base material in conductive material layer surface again, obtain porous silicon composite cathode material, The higher first charge-discharge efficiency that porous silica material itself has not only is utilized, but also is coated on leading for porous silica material surface Electric material can not only increase the electric conductivity of composite material, and porous silica material can also be inhibited, which to expand outward, to be caused to rupture, and improve Cyclical stability；Surface after composite Nano silica-base material, has better cycle performance again, and it is multiple that porous silica material can be improved The cycle performance of condensation material；Further, it is further continued for being mixed with the conductive material on nano silica-base material surface, it can not only The electric conductivity for increasing composite material again, can also alleviate the volume expansion of nano silica-base material, and it is steady to further improve circulation It is qualitative.
The present invention also provides a kind of preparation methods of porous silicon composite cathode material, comprising the following steps:
(1) porous silicon matrix is coated using the first conductive material presoma, then handles 5 at 400~1600 DEG C ~10 hours, obtain the first presoma；
The first conductive material presoma includes conductive carbon material material precursor, conductive carbon material material precursor and alloy material The mixture or alloy material presoma of presoma；
The cladding includes emulsification cladding, liquid phase coating, gas phase cladding or solid phase cladding；
(2) the first presoma and the progress of nano silicon-based raw material is compound, then handled 5~10 hours at 400~1600 DEG C, Obtain porous silicon composite cathode material；
The nano silicon-based raw material includes the mixture of silicon source or silicon source and other raw materials；Other described raw materials include receiving Rice conductive material and/or conductive carbon material material precursor；
It is described compound including emulsification is compound, liquid phase is compound, gaseous recombination or solid phase are compound.
The present invention especially indicates the optimum principles such as the selection of the raw material and ratio, such as nothing, compound with previous porous silicon It is consistent in negative electrode material, or selected and adjusted i.e. accordingly according to the ratio in porous silicon composite cathode material Can, this is no longer going to repeat them.
The present invention coats porous silicon matrix using the first conductive material presoma, then at 400~1600 DEG C Reason 5~10 hours, obtains the first presoma.
The concept of the presoma is not particularly limited in the present invention, prepares the material with well known to those skilled in the art Raw material, those skilled in the art can be selected according to practical condition, quality requirement and properties of product and Adjustment.
The first conductive material presoma is not particularly limited in the present invention, with well known to those skilled in the art first Conductive material prepares raw material, and those skilled in the art can be according to practical condition, quality requirement and product It can be carried out selection and adjustment, the first conductive material presoma of the present invention preferably includes conductive carbon material material precursor, conductive carbon The mixture or alloy material presoma of material precursor and alloy material presoma.
The conductive carbon material material precursor is not particularly limited in the present invention, is led with preparation well known to those skilled in the art The raw material of electrical carbon material, those skilled in the art can according to practical condition, quality requirement and properties of product into Row selection and adjustment, conductive carbon material material precursor of the present invention preferably include sucrose, glucose, phenolic resin and melamine One of formaldehyde, methane and ethylene are a variety of, more preferably sucrose, glucose, phenolic resin and melamino-formaldehyde, methane Or ethylene.It may be direct conductive carbon material, such as graphene, carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, receive Meter Shi Mo, cracking one of carbon and conductive black or a variety of.
The alloy material presoma is not particularly limited in the present invention, is used to prepare with well known to those skilled in the art The source metal of composite negative pole material, those skilled in the art can be according to practical condition, quality requirement and products Performance is selected and is adjusted, and source metal of the present invention preferably includes molysite, aluminium salt, pink salt, mantoquita, titanium salt, manganese salt, germanium One of salt, cobalt salt, zinc salt, magnesium salts, aluminum oxide, stannic oxide, titanium dioxide and copper oxide are a variety of, more preferably Molysite, aluminium salt, pink salt, mantoquita, titanium salt, manganese salt, germanium salt, cobalt salt, zinc salt, magnesium salts, aluminum oxide, stannic oxide, titanium dioxide Two or more in titanium and copper oxide.
The cladding is not particularly limited in the present invention, is coated with method for coating well known to those skilled in the art, Those skilled in the art can select and adjust according to practical condition, quality requirement and properties of product, the present invention The cladding preferably includes liquid phase coating, gas phase cladding or solid phase cladding.
The temperature of the processing is not particularly limited in the present invention, with the temperature of heat treatment well known to those skilled in the art , those skilled in the art can select and adjust according to practical condition, quality requirement and properties of product, this The temperature for inventing the processing is preferably 400~1600 DEG C, more preferably 600~1400 DEG C, most preferably 800~1200 DEG C. The time of the processing is not particularly limited in the present invention, with the time of heat treatment well known to those skilled in the art, originally Field technical staff can select and adjust according to practical condition, quality requirement and properties of product, institute of the present invention The time for stating processing is preferably 5~10 hours, more preferably 6~9 hours, most preferably 7~8 hours.
The detailed process of the processing is not particularly limited in the present invention, with heat treatment well known to those skilled in the art Process, those skilled in the art can select and adjust according to practical condition, quality requirement and properties of product Whole, processing of the present invention is preferably high-temperature heat treatment.When cladding of the present invention is gas phase cladding, the processing can be considered as It is carried out simultaneously with gas phase cladding process, i.e. the pyroprocess of gas phase cladding.Particularly, when the conductive material contains source metal When, the processing is particularly preferred as, and under conditions of reducibility gas, is handled (high-temperature heat treatment).The present invention is to described Reducibility gas is not particularly limited, and with reducibility gas well known to those skilled in the art, those skilled in the art can To be selected and be adjusted according to practical condition, quality requirement and properties of product, reducibility gas of the present invention is excellent Choosing includes ammonia and protective gas；The protective gas preferably includes nitrogen and/or inert gas, more preferably nitrogen or Inert gas.
The present invention is to improve the integrality and operability of technique, and the step (1) is specifically as follows:
Porous silicon and the first conductive material presoma are dispersed with stirring or are dissolved in a solvent, is then spray-dried, obtains Coat product；
The mass ratio of the porous silicon and the first conductive presoma is preferably (1~2): (1~5), more preferably (1~2): (2~4), most preferably (1.3~1.7): (2.5~3.5)；The solvent is preferably one of water, ethyl alcohol, formaldehyde and toluene Or it is a variety of；
The step (1) specifically may be:
By porous silicon and the first conductive material presoma mixing and ball milling preferably 5~for 24 hours, more preferably 10~20h, most preferably For 13~17h；Obtain cladding product；The mass ratio of the porous silicon and the first conductive presoma is preferably (1~2): (1~5), More preferably (1~2): (2~4), most preferably (1.3~1.7): (2.5~3.5)；
The step (1) specifically may be:
By porous silicon preferably at 500~1500 DEG C, more preferably 700~1300 DEG C, most preferably 900~1100 DEG C；Under It is passed through inert gas and the first conductive material presoma, then naturally cools to room temperature, obtains cladding product；The porous silicon with The mass ratio of first conductive presoma is (1~2): (1~5), more preferably (1~2): (2~4), most preferably (1.3~ 1.7): (2.5~3.5)；Inert gas preferably includes nitrogen and/or argon gas；
The step (1) specifically may be:
By porous silicon and the first conductive presoma mixing and ball milling preferably 5~for 24 hours, more preferably 10~20h, most preferably 13 ~17h；Then preferably at 500~1500 DEG C, more preferably 700~1300 DEG C, most preferably 900~1100 DEG C；Under be passed through it is lazy Property gas and reducibility gas preferably 5~20h, more preferably 8~17h, most preferably 10~15h；Cooled to room temperature obtains To cladding product；The mass ratio of the porous silicon and the first conductive presoma is (1~2): (1~5), more preferably (1~2): (2~4), most preferably (1.3~1.7): (2.5~3.5)；The inert gas preferably includes nitrogen and/or argon gas；It is described to go back Originality gas preferably includes hydrogen and/or ammonia；
The step (1) specifically may be:
It disperses porous silicon and the first conductive presoma in the solvent containing emulsifier, it is more excellent preferably at 10~100 DEG C It is selected as 30~80 DEG C, most preferably 50~60 DEG C；Lower stirring 5~20h, more preferably 8~17h, most preferably 10~15h；So Centrifugation obtains cladding product afterwards；The mass ratio of the porous silicon and the first conductive presoma is (1~2): (1~5), more preferably (1~2): (2~4), most preferably (1.3~1.7): (2.5~3.5)；The emulsifier preferably includes polyethylene glycol octyl benzene One of base ether, Span series and twain series emulsifier are a variety of.
The present invention then the first presoma and nano silicon-based raw material are carried out it is compound, then 400~1600 DEG C of processing 5~ 10 hours, obtain porous silicon composite cathode material.
The nano silicon-based raw material is not particularly limited in the present invention, with nano-silicon base well known to those skilled in the art Material, those skilled in the art can select and adjust according to practical condition, quality requirement and properties of product, Nano silicon-based raw material of the present invention preferably includes the mixture of silicon source or silicon source and other raw materials；Other described raw materials are preferred Including nanometer conductive material and/or conductive carbon material material precursor.Before the present invention is to the nanometer conductive material or conductive carbon material Range and the optimum principle for driving body are consistent in aforementioned nanometer conductive material and conductive carbon material material precursor, not another here One repeats；Silicon source of the present invention preferably includes SiH4、Si2H6、Si3H8、SiCl4、SiHCl3、Si2Cl6、SiH2Cl2Or SiH3Cl, or direct nano silica-base material, such as silicon nanoparticle, the oxygen-containing silicon particle of nanometer, nano silicon film and nanometer One of silicon particle is a variety of.It is described when the present invention is to the mixture that the nano silicon-based raw material is silicon source and other raw materials Ratio shared by nano silicon material or the silicon source is not particularly limited, and those skilled in the art can be according to actual production feelings Condition, quality requirement and properties of product are selected and are adjusted, and nano silicon material of the present invention or the silicon source account for described receive The content of rice silica-base material is preferably 40~99.99wt%, preferably 50~90wt%, most preferably 60~80wt%.
The present invention is to improve the integrality and operability of technique, and the step (2) is specifically as follows:
Porous silicon and the first conductive material presoma are dispersed with stirring or are dissolved in a solvent, is then spray-dried, obtains Coat product；
First presoma and nano silicon-based raw material are dispersed with stirring in a solvent, are then spray-dried, combination product is obtained； The mass ratio of first presoma and nano silicon-based raw material is preferably (1~2): (1~5), more preferably (1~2): (2~ 4), most preferably (1.3~1.7): (2.5~3.5)；；The solvent be preferably one of water, ethyl alcohol, formaldehyde and toluene or It is a variety of；
The step (2) specifically may be:
By the first presoma and nano silicon-based raw material mixing and ball milling 5~for 24 hours, more preferably 10~20h, most preferably 13~ 17h；Obtain combination product；The mass ratio of first presoma and nano silicon-based raw material is preferably (1~2): (1~5), more excellent It is selected as (1~2): (2~4), most preferably (1.3~1.7): (2.5~3.5)；
The step (2) specifically may be:
By the first presoma at 500~1500 DEG C, more preferably 700~1300 DEG C, most preferably 900~1100 DEG C；Under It is passed through inert gas and nano silicon-based raw material, then naturally cools to room temperature, obtains combination product；First presoma with receive The mass ratio of rice silyl starting material is preferably (1~2): (1~5), more preferably (1~2): (2~4), most preferably (1.3~ 1.7): (2.5~3.5)；The inert gas preferably includes nitrogen and/or argon gas；
The step (2) specifically may be:
By the first presoma and nano silicon-based stock dispersion in the solvent containing emulsifier, preferably at 10~100 DEG C, more Preferably 30~80 DEG C, most preferably 50~60 DEG C；Lower stirring 5~20h, more preferably 8~17h, most preferably 10~15h； It is then centrifuged for obtaining combination product；The mass ratio of first presoma and nano silicon-based raw material is preferably (1~2): (1~5), More preferably (1~2): (2~4), most preferably (1.3~1.7): (2.5~3.5)；The emulsifier preferably includes poly- second two One of alcohol octyl phenyl ether, Span series and twain series emulsifier are a variety of.
The present invention to it is described it is compound be not particularly limited, it is compound with complex method well known to those skilled in the art, Those skilled in the art can select and adjust according to practical condition, quality requirement and properties of product, the present invention It is described it is compound preferably include to emulsify that compound, liquid phase is compound, gaseous recombination or solid phase are compound, it is multiple more preferably to emulsify compound or gas phase It closes, is specifically as follows emulsification cladding.
The temperature of the processing in the step (2) is not particularly limited in the present invention, with well known to those skilled in the art The temperature of heat treatment, those skilled in the art can carry out according to practical condition, quality requirement and properties of product It selects and adjusts, the temperature of the processing in step (2) of the present invention is preferably 400~1600 DEG C, more preferably 600~1400 DEG C, most preferably 800~1200 DEG C.The time of the processing in the step (2) is not particularly limited in the present invention, with this field The time being heat-treated known to technical staff, those skilled in the art can according to practical condition, quality requirement with And properties of product are selected and are adjusted, the time of the processing in step (2) of the present invention is preferably 5~10 hours, more excellent It is selected as 6~9 hours, most preferably 7~8 hours.
The detailed process of the processing in the step (2) is not particularly limited in the present invention, ripe with those skilled in the art The process for the heat treatment known, those skilled in the art can be according to practical condition, quality requirement and properties of product It is selected and is adjusted, processing is preferably high-temperature heat treatment in step (2) of the present invention.
The silicon source is not particularly limited in the present invention, with silicon source well known to those skilled in the art, this field skill Art personnel can select and adjust according to practical condition, quality requirement and properties of product, silicon source of the present invention Preferably include SiH4、Si2H6、Si3H8、SiCl4、SiHCl3、Si2Cl6、SiH2Cl2And SiH3One of Cl or a variety of, more preferably For SiH4、Si2H6、Si3H8、SiCl4、SiHCl3、Si2Cl6、SiH2Cl2Or SiH3Cl。
Further, the present invention is to improve compound performance, and the compound emulsification is most preferably emulsification cladding.Institute of the present invention Stating step (2) specifically can also be, the first presoma and nano silicon-based raw material emulsify compound and 400 under protective atmosphere ~1600 DEG C are handled 5~10 hours, obtain porous silicon composite cathode material；Or for by the first presoma and nanometer silicon source, receive Rice conductive material and conductive carbon material material precursor emulsify it is compound and after being sintered under protective atmosphere (protective gas), Obtain porous silicon composite cathode material.
The compound emulsifier of emulsification of the present invention can also preferably include anionic emulsifier, cationic emulsification Agent or nonionic emulsifier more specifically can be odium stearate salt, lauryl sodium sulfate salt, calcium dodecyl benzene sulfonate Salt, N- domiphen have polyethenoxy ether class or polyoxypropylene ethers；It is of the present invention to emulsify the milkiness being compounded to form Liquid type preferably include oil-in-water type, water-in-oil type, multiple emulsion, non-aqueous emulsion, liquid-crystal emulsion, color development emulsion, One of gel emulsion and phosphatide emulsion are a variety of, more preferably oil-in-water type, water-in-oil type, multiple emulsion, non- Aqueous emulsion, liquid-crystal emulsion, color development emulsion, gel emulsion or phosphatide emulsion.
Particularly, the present invention is to improve the cycle performance and stability of porous silicon composite cathode material, further preferably to institute It states porous silicon composite cathode material and carries out cladding processing again, i.e., the porous silicon composite cathode material obtained to above-mentioned steps is again Cladding processing is carried out, final porous silicon composite cathode material product is obtained.
The specific steps of the cladding processing are not particularly limited in the present invention, with cladding well known to those skilled in the art Method cladding, those skilled in the art can select according to practical condition, quality requirement and properties of product And adjustment, cladding processing of the present invention preferably includes emulsification cladding, liquid phase coating, gas phase cladding or solid phase cladding, specific to walk It is rapid to be more preferably:
Porous silicon composite cathode material is coated using the second conductive material presoma, then at 400~1500 DEG C Processing 5~10 hours.
As without especially indicating, the present invention is to the detailed process of above-mentioned steps, selection, parameter and preferred scope and aforementioned first Detailed process that conductive material presoma coats porous silicon matrix, selection, parameter are consistent with preferred scope, herein not It repeats one by one again.Selection, parameter and preferred scope and aforementioned first conduction of the present invention to above-mentioned second conductive material presoma The selection of material precursor, parameter are consistent with preferred scope, and this is no longer going to repeat them.Porous silicon Compound Negative of the present invention The mass ratio of pole material and the second conductive presoma is preferably (5~10): 1, more preferably (6~9): 1, most preferably (7~ 8): 1.
After the present invention finally post-processes the semi-finished product that preferred above-mentioned steps obtain, porous silicon composite cathode material is obtained Material.
The mode and step of the post-processing is not particularly limited in the present invention, with routine well known to those skilled in the art Post processing mode and step, those skilled in the art can be according to practical condition, product situation and performance requirements It is adjusted, post-processing of the present invention preferably includes grinding, dry, sieving and except one of magnetic or a variety of, more preferably Grinding, dry, sieving and except a variety of in magnetic, are most preferably ground up, sieved and remove magnetic.The present invention be ground up, sieved to above-mentioned and Except the actual conditions of the postprocessing working procedures such as magnetic are not particularly limited, with above-mentioned postprocessing working procedures well known to those skilled in the art Condition, those skilled in the art can be adjusted according to practical condition, product situation and performance requirement.
Above-mentioned steps of the present invention are prepared for a kind of porous silicon composite cathode material, and the present invention uses conductive material to carry out first It coats for the first time, then continues composite Nano silica-base material in conductive material layer surface again, obtain porous silicon composite cathode material, The higher first charge-discharge efficiency that porous silica material itself has not only is utilized, but also is coated on leading for porous silica material surface Electric material can not only increase the electric conductivity of composite material, and porous silica material can also be inhibited, which to expand outward, to be caused to rupture, and improve Cyclical stability；Surface after composite Nano silica-base material, has better cycle performance again, and it is multiple that porous silica material can be improved The cycle performance of condensation material；Further, it is further continued for being mixed with the conductive material on nano silica-base material surface, it can not only The electric conductivity for increasing composite material again, can also alleviate the volume expansion of nano silica-base material, and it is steady to further improve circulation It is qualitative.Particularly, the present invention is to improve the performance of porous silicon composite cathode material, especially using emulsification composite algorithm to nano silicon-based Material is doped cladding.In addition, preparation method of the invention is easy to operate, safe, versatile, production cost is low, suitable Industrialized production.The experimental results showed that porous silicon composite cathode material of the invention has height ratio capacity (> 1300mAh/g), height First charge-discharge efficiency (> 85%) and high circulation performance (150 circulations, capacity retention ratio are 90% or more).
For a further understanding of the present invention, below with reference to embodiment to a kind of porous silicon composite cathode material provided by the invention Material and preparation method thereof be illustrated, but it is to be understood that these embodiments be under the premise of the technical scheme of the present invention into Row is implemented, and the detailed implementation method and specific operation process are given, only to further illustrate feature of the invention and excellent Point, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
It disperses porous silicon in the solvent dissolved with grape grape, wherein the mass ratio of porous silicon and glucose is 1:1, porous Silicon specific surface area is 40cm2/ g, average particle size are 13 μm.It after being uniformly dispersed, is spray-dried, inlet air temperature is 200 DEG C, out Air temperature is 100 DEG C, and dispersion disk rotating speed is 2000r/min, and then in nitrogen atmosphere, 800 DEG C of carbonization 5h are cooled to room later Temperature obtains the porous silica material of cladding cracking carbon, i.e. the first presoma.
The porous silica material for being coated with cracking carbon is placed in rotary furnace, in the case where high pure nitrogen flow is 5.0L/min, 500 DEG C are warming up to, high pure nitrogen is then become into high-purity hydrogen and SiH4Gaseous mixture, flow remains unchanged, when being passed through silane Gas is changed to high pure nitrogen after being 1:1 by gas and first forerunner's body mass ratio, cooled to room temperature, obtains porous silicon/lead Electric material clad/nano silica-base material composite material.
Embodiment 2 and 3
It is identical in experimental procedure and embodiment 1 in embodiment 2 and 3, only change porous silicon and glucose mass ratio and The mass ratio of first presoma and silane.The mass ratio of porous silicon and glucose is 2:1, the first presoma and silicon in embodiment 2 The mass ratio of alkane is 2:1；The mass ratio of porous silicon and glucose is 2:5, the mass ratio of the first presoma and silane in embodiment 3 For 2:5.
Embodiment 4,5 and 6
Experiment in embodiment 4,5,6 is identical with embodiment 1,2,3 respectively, and silane is only changed to the mixing of silane and methane Gas, wherein the mass ratio of silane and methane is 1:1, the gross mass point of the mixed gas of silane and methane in embodiment 4,5,6 The quality of silane is equal in other and embodiment 1,2,3.
Embodiment 7
It disperses porous silicon in the ethyl alcohol dissolved with phenolic resin, wherein the mass ratio of porous silicon and phenolic resin is 2:1, The specific surface area of porous silicon is 150cm2/ g, average particle size are 15 μm, are spray-dried after mixing, and inlet air temperature is 200 DEG C, Leaving air temp is 100 DEG C, and dispersion disk rotating speed is 2000r/min, and then in nitrogen atmosphere, 800 DEG C of carbonization 5h are cooled to later Room temperature obtains the porous silica material of cladding cracking carbon, i.e. the first presoma.
By the first presoma be scattered in containing nano-silicon, melamine, Triton X-100 alcohol in, revolving speed For 500rmp, wherein the mass ratio of porous silicon and nano-silicon, melamine is 2:0.5:0.5, and the average grain diameter of nano-silicon is 80nm later pours into dispersion liquid in the paraffin oil containing sorbester p17, and 1h, revolving speed 500rmp are vigorously stirred at 60 DEG C, it Continue at 100 DEG C afterwards stir 10h, the solid deionized water and ethanol wash that will be obtained by filtration, then in nitrogen atmosphere, 800 DEG C of heating 5h, cooled to room temperature, obtains porous silicon/conductive material clad/nano silica-base material composite wood later Material, i.e. semi-finished product.
After the sieving of this semi-finished product composite material, it is fitted into planetary ball mill after being mixed with copper oxide, is packed into the zirconium of 1mm Pearl then passes to argon gas protective gas, carries out ball milling, and wherein drum's speed of rotation is 400r/min, the mass ratio of abrading-ball and powder For 50:1, the mass ratio of semi-finished product and copper oxide is 5:1, after ball milling 10h, obtains ball milling mixing powder, powder is put into tubular type In furnace, it is heated to 300 DEG C in nitrogen atmosphere, then passes to the mixed gas of ammonia and nitrogen, gas is switched to by constant temperature 3h High pure nitrogen and then cooled to room temperature, this composite material is crossed and screens out magnetic, obtains final porous silicon-base composite negative pole material Expect product.
Referring to Fig. 1, Fig. 1 is the scanning electron microscope of porous silicon composite cathode material prepared by the embodiment of the present invention 7 (SEM) picture.It may be seen that porous silicon composite cathode material is in spherical particle, median particle diameter is 15 μm, particle surface packet Coating is fine and close.
Referring to fig. 2, Fig. 2 is the first charge-discharge curve of porous silicon composite cathode material prepared by the embodiment of the present invention 7.By Figure is as it can be seen that the porous silicon composite cathode material first discharge specific capacity of the preparation of embodiment 7 is higher.
Referring to Fig. 3, the cycle performance curve for the porous silicon composite cathode material that Fig. 3 is prepared for the embodiment of the present invention 7,150 After secondary circulation, capacity retention ratio 92.3%, it is seen that it has preferable cycle performance.
Referring to fig. 4, Fig. 4 is the variation of the efficiency for charge-discharge of porous silicon composite cathode material prepared by the embodiment of the present invention 7 Curve.As seen from the figure, first charge discharge efficiency 88.5%, and it is rapidly reached 99.4% after 5 circulations, in cyclic process In, efficiency keeps stablizing.
Embodiment 8
Embodiment 8 is identical with the experiment in embodiment 7, is only changed to the step of last copper clad semi-finished product with oxidation as follows Step:
Semi-finished product and glucose are dispersed in water, wherein the mass ratio of semi-finished product and glucose is 5:1；After mixing Spray drying, inlet air temperature are 200 DEG C, and leaving air temp is 100 DEG C, and dispersion disk rotating speed is 2000r/min, then in nitrogen atmosphere In, 800 DEG C of carbonization 5h are cooled to room temperature later, obtain final porous silicon-base composite negative pole material product.
Embodiment 9 and 10
It is identical in experimental procedure and embodiment 7 in embodiment 9 and 10, only change the mass ratio of semi-finished product and copper oxide. The mass ratio of semi-finished product and copper oxide is 7:1 in embodiment 9；The mass ratio of semi-finished product and copper oxide is 10:1 in embodiment 10.
It is the cycle performance curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 9 referring to Fig. 5, Fig. 5.By Fig. 5 is it is found that after 150 circulations, and capacity retention ratio 92.4%, cycle performance is higher.
It is the efficiency for charge-discharge curve of porous silicon-base composite negative pole material prepared by the embodiment of the present invention 9 referring to Fig. 6, Fig. 6. It will be appreciated from fig. 6 that its for the first time cycle efficieny be 87.3%, and 6 times circulation after be rapidly reached 99.4%, in cyclic process In, efficiency keeps stablizing.
Embodiment 11 and 12
It is identical in experimental procedure and embodiment 8 in embodiment 11,12, only the mass ratio of semi-finished product and glucose is distinguished Become 7:1 and 10:1.
The Electrochemical results of porous silicon composite cathode material prepared by embodiment 1~12 are as shown in table 1
The electro-chemical test of porous silicon composite cathode material prepared by 1 embodiment 1~12 of table
A kind of porous silicon composite cathode material provided by the invention and preparation method thereof is described in detail above, Used herein a specific example illustrates the principle and implementation of the invention, and the explanation of above embodiments is only used In facilitating the understanding of the method and its core concept of the invention, including best mode, and but also this field any technology people Member can practice the present invention, including any device or system of manufacture and use, and implement the method for any combination.It should refer to It out, for those skilled in the art, without departing from the principle of the present invention, can also be to the present invention Some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.The invention patent The range of protection is defined by the claims, and may include those skilled in the art it is conceivable that other embodiments.If These other embodiments, which have, is not different from the structural element of claim character express, or if they include and right It is required that equivalent structural elements of the character express without essence difference, then these other embodiments should also be included in claim In range.

Claims (10)

1. a kind of porous silicon composite cathode material, which is characterized in that including porous silicon matrix, be compounded in the porous silicon-base body surface First conductive material layer in face, and it is compounded in the nano silica-base material of the first conductive material layer surface.
2. porous silicon composite cathode material according to claim 1, which is characterized in that further include being compounded in the nano-silicon Second outer layer of conductive material on sill surface.
3. porous silicon composite cathode material according to claim 2, which is characterized in that the porous silicon matrix is porous silicon Particle；
The nano silica-base material includes the mixture of silicon nanoparticle and nanometer conductive material, the oxygen-containing silicon particle of nanometer and nanometer One of mixture and silicon nanoparticle of conductive material are a variety of；
The mass ratio of the nano silica-base material and the porous silicon matrix is (1 ~ 2): (3 ~ 12).
4. porous silicon composite cathode material according to claim 2, which is characterized in that first conductive material includes leading The mixture or alloy material of electrical carbon material, conductive carbon material and alloy material；
The mass ratio of first conductive material and the porous silicon matrix is 1:(3 ~ 12)；
Second conductive material includes the mixture or alloy material of conductive carbon material, conductive carbon material and alloy material；Institute The mass ratio for stating the second conductive material and the porous silicon matrix is 1:(3 ~ 12)；
The alloy material includes metallic element alloy and/or metallic element and nonmetalloid alloy.
5. porous silicon composite cathode material according to claim 4, which is characterized in that the conductive carbon material includes graphite Alkene, carbon nanotube, carbon nanocoils, carbon fiber, electrically conductive graphite, cracking one of carbon and conductive black or a variety of.
6. a kind of preparation method of porous silicon composite cathode material, which comprises the following steps:
(1) porous silicon matrix is coated using the first conductive material presoma, it is then small in 400 ~ 1600 DEG C of processing 5 ~ 10 When, obtain the first presoma；
The first conductive material presoma includes conductive carbon material material precursor, conductive carbon material material precursor and alloy material forerunner The mixture or alloy material presoma of body；
The cladding includes emulsification cladding, liquid phase coating, gas phase cladding or solid phase cladding；
(2) the first presoma and the progress of nano silicon-based raw material is compound, it then handles 5 ~ 10 hours, obtains more at 400 ~ 1600 DEG C Hole silicon composite cathode material；
The nano silicon-based raw material includes the mixture of silicon source or silicon source and other raw materials；Other described raw materials are led including nanometer Electric material and/or conductive carbon material material precursor；
It is described compound including emulsification is compound, liquid phase is compound, gaseous recombination or solid phase are compound.
7. preparation method according to claim 6, which is characterized in that carried out again to the porous silicon composite cathode material Cladding processing；
It is described to carry out cladding processing again specifically: porous silicon composite cathode material is carried out using the second conductive material presoma Then cladding is handled 5 ~ 10 hours at 400 ~ 1500 DEG C；
The second conductive material presoma includes conductive carbon material material precursor, conductive carbon material material precursor and alloy material forerunner The mixture or alloy material presoma of body；
The cladding includes emulsification cladding, liquid phase coating, gas phase cladding or solid phase cladding；
The mass ratio of the porous silicon composite cathode material and the second conductive material presoma is (5 ~ 10): 1.
8. preparation method according to claim 6 or 7, which is characterized in that the conductive carbon material material precursor include sucrose, One of glucose, phenolic resin, melamino-formaldehyde, methane and ethylene are a variety of；
The alloy material presoma includes molysite, aluminium salt, pink salt, mantoquita, titanium salt, aluminum oxide, stannic oxide, titanium dioxide One of titanium and copper oxide are a variety of；
The silicon source includes SiH4、Si2H6、Si3H8、SiCl4、SiHCl3、Si2Cl6、SiH2Cl2And SiH3One of Cl or more Kind.
9. preparation method according to claim 6, which is characterized in that cladding in the step (1) specifically:
Porous silicon and the first conductive material presoma are dispersed with stirring or are dissolved in a solvent, is then spray-dried, is coated Product；
The mass ratio of the porous silicon and the first conductive material presoma is (1 ~ 2): (1 ~ 5)；The solvent is water, ethyl alcohol, first One of aldehyde and toluene are a variety of；
Or are as follows:
By porous silicon and the first conductive material presoma mixing and ball milling 5 ~ for 24 hours, cladding product is obtained；The porous silicon is led with first The mass ratio of electric material presoma is (1 ~ 2): (1 ~ 5)；
Or are as follows:
Porous silicon is passed through to inert gas and the first conductive material presoma at 500 ~ 1500 DEG C, then naturally cools to room Temperature obtains cladding product；The mass ratio of the porous silicon and the first conductive material presoma is (1 ~ 2): (1 ~ 5)；Inert gas Including nitrogen and/or argon gas；
Or are as follows:
By porous silicon and the first conductive material presoma mixing and ball milling 5 ~ for 24 hours, inert gas then is passed through at 500 ~ 1500 DEG C With 5 ~ 20h of reducibility gas, cooled to room temperature obtains cladding product；The porous silicon and the first conductive material presoma Mass ratio be (1 ~ 2): (1 ~ 5)；The inert gas includes nitrogen and/or argon gas；The reducibility gas include hydrogen and/ Or ammonia；
Or are as follows:
Disperse porous silicon and the first conductive material presoma in the solvent containing emulsifier, at 10 ~ 100 DEG C stir 5 ~ 20h is then centrifuged for obtaining cladding product；The mass ratio of the porous silicon and the first conductive material presoma is (1 ~ 2): (1 ~ 5)； The emulsifier includes one of Triton X-100, Span series emulsifier and twain series emulsifier or more Kind.
10. preparation method according to claim 6, which is characterized in that compound in the step (2) specifically:
First presoma and nano silicon-based raw material are dispersed with stirring in a solvent, are then spray-dried, combination product is obtained；It is described The mass ratio of first presoma and nano silicon-based raw material is (1 ~ 2): (1 ~ 5)；The solvent is in water, ethyl alcohol, formaldehyde and toluene It is one or more；
Or are as follows:
By the first presoma and nano silicon-based raw material mixing and ball milling 5 ~ for 24 hours, combination product is obtained；First presoma and nanometer The mass ratio of silyl starting material is (1 ~ 2): (1 ~ 5)；
Or are as follows:
First presoma is passed through inert gas and nano silicon-based raw material at 500 ~ 1500 DEG C, then naturally cools to room temperature, Obtain combination product；The mass ratio of first presoma and nano silicon-based raw material is (1 ~ 2): (1 ~ 5)；The inert gas packet Include nitrogen and/or argon gas；
Or are as follows:
By the first presoma and nano silicon-based stock dispersion in the solvent containing emulsifier, 5 ~ 20h is stirred at 10 ~ 100 DEG C, It is then centrifuged for obtaining combination product；The mass ratio of first presoma and nano silicon-based raw material is (1 ~ 2): (1 ~ 5)；The cream Agent includes one of Triton X-100, Span series emulsifier and twain series emulsifier or a variety of.
CN201611177897.0A 2016-12-19 2016-12-19 A kind of porous silicon composite cathode material and preparation method thereof Active CN106711415B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611177897.0A CN106711415B (en) 2016-12-19 2016-12-19 A kind of porous silicon composite cathode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611177897.0A CN106711415B (en) 2016-12-19 2016-12-19 A kind of porous silicon composite cathode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106711415A CN106711415A (en) 2017-05-24
CN106711415B true CN106711415B (en) 2019-05-10

Family

ID=58938324

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611177897.0A Active CN106711415B (en) 2016-12-19 2016-12-19 A kind of porous silicon composite cathode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106711415B (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11362327B2 (en) 2017-09-05 2022-06-14 Institute Of Physics, Chinese Academy Of Sciences Double layer-coated nano-silicon negative electrode material, a method for preparing the same and use thereof
CN108682796A (en) * 2018-04-09 2018-10-19 合肥国轩高科动力能源有限公司 A kind of silicon-carbon cathode material and preparation method thereof of alloying substance cladding
CN109659549B (en) * 2019-01-14 2021-02-12 北京科技大学 Preparation method of multi-stage structure silicon-porous carbon composite negative electrode material for lithium battery
CN110416515B (en) * 2019-07-24 2022-03-04 东莞东阳光科研发有限公司 Lithium ion battery, lithium ion battery cathode material and preparation method
CN110400928A (en) * 2019-08-13 2019-11-01 上海电气集团股份有限公司 A kind of preparation method of silicon based composite material
US11367863B2 (en) * 2019-11-15 2022-06-21 International Business Machines Corporation Porous silicon anode for rechargeable metal halide battery
CN114824183B (en) * 2021-01-22 2024-03-22 上海昱瓴新能源科技有限公司 Method for synthesizing three-dimensional porous silicon powder by silane and application thereof
CN113764622B (en) * 2021-09-13 2023-03-10 合肥国轩高科动力能源有限公司 Preparation method of low-expansion lithium battery silicon-carbon negative plate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474631A (en) * 2013-10-08 2013-12-25 深圳市贝特瑞新能源材料股份有限公司 Silicon monoxide composite negative electrode material for lithium ion battery, preparation method and lithium ion battery
CN105070894A (en) * 2015-07-31 2015-11-18 深圳市贝特瑞新能源材料股份有限公司 Porous silicon-based composite anode material for lithium ion battery and preparation method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101826391B1 (en) * 2015-03-31 2018-02-06 주식회사 엘지화학 Porous silicon-silicon oxide-carbon composite, and preparing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103474631A (en) * 2013-10-08 2013-12-25 深圳市贝特瑞新能源材料股份有限公司 Silicon monoxide composite negative electrode material for lithium ion battery, preparation method and lithium ion battery
CN105070894A (en) * 2015-07-31 2015-11-18 深圳市贝特瑞新能源材料股份有限公司 Porous silicon-based composite anode material for lithium ion battery and preparation method and application

Also Published As

Publication number Publication date
CN106711415A (en) 2017-05-24

Similar Documents

Publication Publication Date Title
CN106711415B (en) A kind of porous silicon composite cathode material and preparation method thereof
CN104953122B (en) Nano-silicone wire/carbon composite negative pole material and preparation method and its lithium ion battery
CN109256535B (en) Silicon @ carbon composite material with yolk shell structure and preparation and application thereof
CN107611406B (en) Preparation method of silicon/graphene/carbon composite negative electrode material
CN104362311B (en) Silicon-carbon composite microsphere anode material and preparation method thereof
CN106252651B (en) A kind of porous composite negative pole material of lithium ion battery and preparation method thereof
CN110085842A (en) A kind of silicon-carbon composite cathode material and preparation method thereof
CN105336940B (en) A kind of sodium titanate nano wire/graphene composite negative pole material and preparation method thereof
CN107293700A (en) A kind of lithium ion battery anode active material and preparation method thereof, negative pole and battery
CN103474667A (en) Silicon-carbon composite negative electrode material for lithium ion battery and preparation method thereof
CN107706398B (en) Preparation method of negative electrode material of silicon-based lithium ion battery
CN106711432B (en) A kind of tridimensional network MoO2Nano material and its preparation and application
CN103078087B (en) A kind of preparation method of lithium titanate/carbon nano tube composite cathode material
TW201824622A (en) Anode slurry for lithium ion battery
KR102629191B1 (en) Silicon-based anode materials for lithium-ion batteries and their manufacturing methods and batteries
CN107579227A (en) Preparation method, silicon-carbon cathode piece and the lithium ion battery of silicon-carbon cathode piece
CN113059174B (en) Preparation method of two-dimensional metal antimony nanosheet
CN108091856A (en) A kind of boehmite coated graphite composite negative pole material, preparation method and the usage
CN107230781A (en) A kind of three-dimensional globular silicon-carbon composite cathode material and preparation method thereof
CN106058179A (en) Preparation method of carbon nanotube/silica/carbon composite cathode material
CN109119618A (en) A kind of nucleocapsid negative electrode material of lithium ion battery double-coating and preparation method thereof
CN108172838A (en) A kind of preparation method and application of graphene coating copper foil current collector
CN104393266A (en) Silicon-carbon composite electrode material of core-shell structure and preparation method thereof
CN108183204A (en) A kind of silicon nanometer sheet-graphene nanometer sheet composite material and preparation and application
Yang et al. Novel three-dimensional tin/carbon hybrid core/shell architecture with large amount of solid cross-linked micro/nanochannels for lithium ion battery application

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant