CN107275590A - A kind of porous Si-C composite material and its preparation method and application - Google Patents
A kind of porous Si-C composite material and its preparation method and application Download PDFInfo
- Publication number
- CN107275590A CN107275590A CN201710356888.6A CN201710356888A CN107275590A CN 107275590 A CN107275590 A CN 107275590A CN 201710356888 A CN201710356888 A CN 201710356888A CN 107275590 A CN107275590 A CN 107275590A
- Authority
- CN
- China
- Prior art keywords
- porous
- composite material
- negative electrode
- cell negative
- preparation
- 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.)
- Pending
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
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of porous Si-C composite material and its preparation method and application.The porous Si-C composite material is composited by porous silicon and carbon material, and carbon material is coated on the surface of porous silicon, and the particle diameter of described porous Si-C composite material is 1 μm 10 μm, and specific surface area is 10 30m2/g.The material is first to obtain porous silicon by mechanical ball mill and acid etch by ferro-silicium, after being combined with organic carbon source by the method for pelletizing of spraying, then is carbonized what is obtained at high temperature.The porous Si-C composite material can be used for preparing GND active material, and it is when being applied to lithium ion battery, shows high coulombic efficiency, high power capacity and superior cyclical stability.
Description
Technical field
Prepared the present invention relates to lithium ion battery anode active material and applied technical field, and in particular to a kind of porous silicon
Carbon composite and preparation method thereof and its application in the battery.
Background technology
With the development of industrial technology, the energy human lives various aspects all in occupation of more and more important position,
Demand to the energy is also increasing.Traditional fossil fuel such as coal, oil, natural gas are while playing an important role
It also show the limitation of itself.National governments have all put into very big energy development New Energy Industry, for example：Solar energy, wind
Can, tide energy etc..Lithium ion battery is as a kind of reliable energy storage means, and since the advent of the world is exactly the focus of research.At present,
The lithium ion battery negative material of commercialization uses carbon materials, and it has, and cycle efficieny is high, have extended cycle life, electrode electricity
The advantages of position is relatively low.With new-energy automobile, wind energy, solar energy storage, intelligent grid energy storage with conversion etc. field it is huge
Big application market is progressively clear, and power lithium-ion battery receives unprecedented concern.Graphite negative electrodes material power lithium from
There is many deficiencies in sub- battery, it is impossible to meet the demand of high-power lithium battery.
Lithium ion battery negative material is naturally ground as the key factor for improving the energy content of battery and cycle life
The favor for the person of studying carefully.Compared with other negative materials, the lithium storage content of silicon based anode material is up to 3579mAh/g, with relatively low
Removal lithium embedded current potential (<0.5V vs.Li/Li+), the advantages of cheap, therefore once proposition just by the extensive concern of researcher
And as study hotspot, be expected to turn into commercialization material.However, researcher has found silicon based anode material meeting during removal lithium embedded
Occur serious Volume Changes (volumetric expansion is more than 300%), cause the problems such as electrode efflorescence, peeling to lead due to Volume Changes
Performance is caused drastically to decline, cycle performance is poor.Meanwhile, the coulombic efficiency first of silicon based anode material is relatively low, silicon intrinsic conductivity
Low, the SEI films of formation are unstable easily to come off.These shortcomings limit its practical application in lithium ion battery
At present, this area still lacks a kind of coulombic efficiency height, and theoretical capacity is high, and cost is low, the negative pole of good cycling stability
Material.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of coulombic efficiency is high, theoretical specific capacity is high, circulating battery is stable
Good porous Si-C composite material of property and its preparation method and application.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes：
The invention provides a kind of porous Si-C composite material, described porous Si-C composite material is by porous silicon and carbon materials
Material is composited, and carbon material is coated on the surface of porous silica material；The particle diameter of the porous Si-C composite material is 1 μm -10 μm,
Specific surface area is 10-30m2/g。
The preparation method of the porous Si-C composite material of the present invention comprises the following steps：
1) ferro-silicium is obtained into silicone content in porous silica material, described ferro-silicium by mechanical ball mill and acid etch
For 70wt%~80wt%, the content of metal impurities is 20wt%~30wt%, described mechanical ball mill include wet ball grinding or
Dry ball milling, and the rotational speed of ball-mill used is 200r/min~500r/min, Ball-milling Time is 1h~64h, and ratio of grinding media to material is 1:1~
20:1；
2) above-mentioned porous silica material and organic carbon source are mixed with suspension with certain proportion in deionized water, by institute
The suspension stated carries out spraying pelletizing processing under spray dryer, and high temperature cabonization under an inert atmosphere, is finally produced afterwards
The porous Si-C composite material of thing.
In above-mentioned technical proposal, further, the organic carbon source includes sucrose, glucose, citric acid or chitin.
Further, the mass ratio of described porous silica material and organic carbon source is selected from the group：4:1,7:3,3:2,1:
1,2:3.
Further, described carbonization inert atmosphere includes argon gas, nitrogen or argon hydrogen mixed atmosphere.
Further, described carburizing temperature is selected from the group：500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C,
800 DEG C, 850 DEG C, 900 DEG C.
It is another object of the present invention to provide the porous Si-C composite material in preparing in chemical energy storage device
Purposes.Wherein, the chemical energy storage device includes but is not limited to battery.
It is yet a further object of the present invention to provide a kind of cell negative electrode material, the material is with the porous silicon-carbon of the present invention
Composite as cell negative electrode material main active.
Further, described porous Si-C composite material content is 60wt%~80wt%.
Further, described cell negative electrode material also includes conductive agent and/or adhesive.
Further, 10wt%~20wt% conductive agents are included in described cell negative electrode material.
Further, 10wt%~20wt% adhesives are included in described cell negative electrode material.
Further, described cell negative electrode material includes porous Si-C composite material, conductive agent and adhesive, and three
Mass ratio can be (70 ± 10):(10±2):(20±2).
It is yet a further object of the present invention to provide a kind of battery, it include positive electrode, negative material, electrolyte and every
Film, wherein, the negative material includes described porous Si-C composite material or any of the above-described kind of cell negative electrode material.
It is yet a further object of the present invention to provide a kind of device, it includes described porous Si-C composite material, described
Cell negative electrode material or described battery.
Compared with prior art, advantages of the present invention at least includes：
(1) present invention is successfully prepared a kind of porous Si-C composite material for being applicable as GND active material, should
The features such as coulombic efficiency is high, theoretical specific capacity is high, circulating battery stability is good is shown during used in lithium ion battery, better than existing
Same type of material in technology；
(2) the porous Si-C composite material preparation technology that the present invention is provided is simple, only needs conventional equipment to implement, and institute
Cheap and easy to get with raw material, technical process is easily controllable, and repeatability is good, and yield is high, and product quality is stable, is adapted to extensive raw
Production.
More detailed explanation will hereafter be made to technical scheme.It is understood, however, that in model of the present invention
, can between above-mentioned each technical characteristic of the invention and each technical characteristic specifically described in below (eg embodiment) in enclosing
It is combined with each other, so as to constitute new or preferred technical scheme.As space is limited, no longer tire out one by one herein and state.
Brief description of the drawings
Fig. 1 is the XRD of prepared porous Si-C composite material in the embodiment of the present invention 1；
Fig. 2 is the Raman collection of illustrative plates of prepared porous Si-C composite material in the embodiment of the present invention 1；
Fig. 3 is the SEM figures of prepared porous Si-C composite material in the embodiment of the present invention 1；
Fig. 4 is the cycle performance curve map based on the porous silicon C-C composite electrode in the embodiment of the present invention 1.
Embodiment
As it was previously stated, in view of many deficiencies of prior art, inventor's in-depth study and a large amount of by long-term
Practice, is able to propose technical scheme, as detailed below.
Porous Si-C composite material
The first aspect of the present invention provides a kind of porous Si-C composite material, and it is mainly with ferro-silicium and organic carbon
Source is prepared from for raw material.
Described porous Si-C composite material is composited by porous silicon and carbon material, and carbon material is coated on porous silicon
Surface, size is micron level, and particle size range is 1-10 μm, and specific surface area is 10-30m2/ g, described porous silicon-carbon is combined
Material has the reaction phase that can be reacted with lithium (Li).
Ferro-silicium material is strained in the present invention by mechanical ball mill and acid etch process, defect simultaneously forms porous
Structure, by spray pelletizing and high temperature cabonization in one layer of carbon material of Surface coating of porous silica material, can effectively improve porous
Huge volumetric expansion problem during the cycle performance of Si-C composite material and effectively alleviation alloying with silicon.
The preparation method of porous Si-C composite material
The porous Si-C composite material preparation method includes：Sonochemical method, wet chemical method, mechanico-chemical reaction
(such as mechanical alloying method and mechanical attrition method), spray pelletizing, high temperature cabonization etc..
Among a preferred embodiment, a kind of porous Si-C composite material preparation method includes：Ferro-silicium and to have
Machine carbon source is raw material, and target product is made by mechanical ball mill, acid etch, spraying pelletizing and high temperature cabonization.
Among one more specifically embodiment, the preparation method may include steps of：
(1) the metallurgy iron silicon materials of silicon source are provided；
(2) described ferro-silicium is subjected to mechanical ball mill；
(3) the metal auxiliary acid etch of ferro-silicium is carried out in acid etch reagent, porous silica material is made.
(4) porous silica material and organic carbon source are mixed to form suspension in deionized water.
(5) spraying pelletizing processing is carried out to the suspension formed using spray dryer.
(6) to dried product high temperature cabonization under an inert atmosphere, the porous Si-C composite material of final products is obtained.
In described metallurgical ferro-silicium, the weight/mass percentage composition of silicon is about 70-80wt%, with the gross weight of the alloy
Meter.
Described mechanical ball mill include wet ball grinding or dry ball milling, and the rotational speed of ball-mill used for 200r/min~
500r/min, Ball-milling Time is 1h~64h, and ratio of grinding media to material is 1:1~20:1；
Described organic carbon source includes sucrose, glucose, citric acid or chitin.
Described porous Si-C composite material and the ratio of organic carbon source are selected from the group：4:1,7:3,3:2,1:1,2:3.
Described carbonization inert atmosphere includes argon gas, nitrogen or argon hydrogen mixed atmosphere.
Described carburizing temperature is selected from the group：500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850
DEG C, 900 DEG C.
Among one more specifically case study on implementation, one kind prepares porous silicon using ferro-silicium and organic carbon source as raw material
The method of carbon composite specifically includes following steps：
(i) weigh a certain amount of industrial ferro-silicium and be put into ball grinder, add solvent, finally weigh a certain amount of abrading-ball,
The mass ratio of abrading-ball, solvent and ferro-silicium is set as 1：2：6；
(ii) with the above-mentioned sample of 300r/min rotating speed ball milling 12 hours；
(iii) ferro-silicium after ball milling is subjected to pickling 12h with 2M hydrochloric acid solution；Then the hydrogen fluorine of concentration 10% is used
The oxide layer 6h that acid cleaning surface is present, through row suction filtration, porous silica material is made in cleaning；
(iv) by porous silica material and organic carbon source in mass ratio 1:1 is mixed to form suspension in deionized water.
(v) suspension is carried out to spraying pelletizing processing under spray dryer.
(vi) compound formed is carbonized in argon gas atmosphere under 700 DEG C of high temperature.Material is made many through row suction filtration, cleaning
Hole Si-C composite material.
Wherein, the ferro-silicium can be bought by commercially available approach.
Wherein, step (iii) and the material described in (vi) can pass through water or the multiple filtering and washing of ethanol.
In the preparation technology of the present invention, make the performance of material by carrying out mechanical ball mill processing to ferro-silicium particle first
Change, the porous silica material with special appearance and structure is formd by acid etch again afterwards, afterwards and organic carbon source
Composite is formed in spraying balling process, by the porous silica material of high temperature cabonization formation carbon coating under inert atmosphere.Should
Porous Si-C composite material in the negative active core-shell material applied to lithium ion battery, show high coulombic efficiency, high power capacity and
The features such as superior cyclical stability.
Battery containing negative active core-shell material
The porous Si-C composite material of the present invention can apply to chemical energy storage device, such as field of batteries.
Among an embodiment, a kind of product contains described porous Si-C composite material or the product by described
Porous Si-C composite material is made.The product includes lithium ion battery or cell negative electrode material.
Among an embodiment, a kind of GND active material is including described porous Si-C composite material or by institute
The porous Si-C composite material stated is made.
Among an embodiment, a kind of negative material is used as negative electrode active material comprising described porous Si-C composite material
Material.
In another preference, the negative material also includes conductive agent and/or adhesive.
In another preference, among the negative material, the content of the porous Si-C composite material is 60-
80wt%.With the gross weight meter of negative material.
Among an embodiment, a kind of battery includes positive electrode, negative material, electrolyte and barrier film, and the negative pole
Material is used as negative active core-shell material comprising described porous Si-C composite material.
Among an embodiment, described negative material is main by the porous Si-C composite material, conductive agent and coheres
Agent is constituted.
More preferred, among the negative material, the content of porous Si-C composite material is 60-80wt%, conductive
The content of agent is 10-20wt%, and the content of adhesive is 10-20wt%.
Wherein, described adhesive includes the polymeric derivative with carboxyl, but not limited to this.
In another preference, described battery also has shell, and the material of the shell is not particularly limited, Ke Yishi
Metal material, non-metal inorganic material, organic material or other composites etc..
In another preference, the battery is preferably non-aqueous battery.
Further, described barrier film can be any one existing battery diaphragm of this area, such as polytetrafluoroethylene (PTFE) every
Film, ceramic porous membrane, fibreglass diaphragm etc., and not limited to this.
Among an embodiment, the electrolyte include one or more kinds of electrolytic salts and/or it is one or two kinds of with
Upper solvent.
In another preference, described electrolytic salt includes cation, for example, can use lithium salts.It is preferred that lithium salts bag
Include lithium hexafluoro phosphate, lithium perchlorate, lithium chloride, lithium bromide etc., but not limited to this.
In another preference, the battery is lithium battery, and the electrolytic salt is selected from lithium salts, but not limited to this.
In another preference, the electrolytic salt meets following require：In charging process, the electrolytic salt is just
Ion can pass through electrolyte, and negative material is reached from positive electrode, and in discharge process, the cation of the electrolytic salt
Electrolyte can be passed through, positive electrode is reached from negative material.
It is described preferred solvents organic solvent in another preference, such as including but not limited to methyl ethyl carbonate
Ester (Methyl Ethyl Carbonate), dimethyl carbonate (Dimethyl Carbonate), diethyl carbonate (Diethyl
Carbonate), ethylene carbonate (Ethylene Carbonate), propene carbonate (Propylene Carbonate), 1,
2- dimethoxy-ethanes, 1,3 dioxolanes, methyl phenyl ethers anisole, acetic acid esters, propionic ester, butyrate, diethyl ether, acetonitrile, propionitrile.
In another preference, the organic solvent includes at least one ring-type replaced by one or more halogen atoms
The amyl- 2- ketone of fluoro- 1, the 3- dioxanes of carbonic acid ester derivative, such as 4-, but not limited to this, it can improve the cyclicity of electrode
Energy.
The electrolyte solvent can be used alone, and can also include two kinds or multi-solvents, electrolytic salt can be single
Solely use, can also include two kinds or a variety of lithium salts.
Postscript, inventor has found through many experiments, when with the porous Si-C composite material of the present invention directly as negative
Pole active material and foregoing various electrolyte, when particularly various lithium-ion battery electrolytes coordinate, show high coulomb
The features such as efficiency, high charge-discharge specific capacity and circulating battery stabilised efficiency, show the porous Si-C composite material tool of the present invention
There is quite good universality.
Described positive electrode has no particular limits, and may be referred to state of the art and is selected, or using this
The existing positive electrode in field.
In a preference, described positive electrode includes one or more reactive metal oxides as positive-active
Also include the inactive metal element being selected from the group in material, and described reactive metal oxides：Manganese (Mn), iron (Fe), cobalt
(Co), vanadium (V), nickel (Ni), chromium (Cr), or its combination, and not limited to this.
It is preferred that described positive electrode also includes the component being selected from the group：Metal oxide, the metal of inactive metal
Sulfide, transition metal oxide, transient metal sulfide, or its combination, and not limited to this.
In another preference, foregoing active metal is lithium.
In another preference, when described battery is lithium battery, described positive electrode also includes what is be selected from the group
Component：
LiMnO2,
LiMn2O4,
LiCoO2,
Li2CrO7,
LiNiO2,
LiFeO2,
LiNixCo1-XO2(0<x<1),
LiFePO4,
LiMnzNi1-ZO2(0<z<1, such as LiMn0.5Ni0.5O2),
LiMn0.33Co0.33Ni0.33O2,
LiMc0.5Mn1.5O4, Mc is divalent metal；
LiNixCoyMezO2, Me represents one kind or several elements in Al, Mg, Ti, B, Ga, Si, x>0；y<1, z<1,
Transition metal oxide,
Transient metal sulfide,
Or its combination.
Wherein, the transition metal oxide preferably from but be not limited to MnO2、V2O5Deng.
Wherein, the transient metal sulfide preferably from but be not limited to FeS2、MoS2、TiS2Deng.
Wherein, lithium ion transition metal oxide has obtained more applications, more preferred, and it can be selected from
LiMn2O4, LiCoO2, LiNi0.8Co0.15Al0.05O2, LiFePO4And LiNi0.33Mn0.33Co0.33O2In one or more, and not
It is limited to this.
The present invention is expanded on further below in conjunction with specific embodiment.It should be understood that these embodiments are merely to illustrate this hair
Bright rather than limitation the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to routine
Condition, or according to the condition proposed by manufacturer.Postscript, unless otherwise indicated, otherwise following percentage and number are pressed
Weight is calculated.
Embodiment 1
The preparation of porous Si-C composite material：
1) the metallurgical ferro-siliciums of 5g, 10g absolute ethyl alcohols and 30g agate abrading-balls are weighed, 200ml agate materials are added separately to
Ball grinder.
2) ball grinder is put into ball mill, sets ball milling parameter, rotating speed 300r/min, working time 12h often work
20min rests 10min.
3) by the good form of small iron particles silicon alloy suction filtration of ball milling, washing, drying.
4) hydrochloric acid solution for measuring 100ml 2M is put into 200ml beaker, is slowly added to form of small iron particles silicon alloy, not
Disconnected stirring is finished until adding.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.Beaker is removed to be placed on magnetic stirring apparatus
Continuously stir 24h.Suction filtration, drying.
5) it will be added to by the sample of HCl treatment in the hydrofluoric acid solution of concentration 10%, persistently stir 24h.Suction filtration,
Washing, drying, are made porous silica material.
6) the porous silica material 2g and sucrose 2g prepared is weighed, is added in 100ml deionized water, stirring forms outstanding
Turbid liquid.
7) suspension is spray-dried, forms the composite of porous silicon/organic carbon source.
8) composite of porous silicon/organic carbon source carries out high temperature cabonization for 700 DEG C under an inert atmosphere, obtains porous silicon-carbon
Composite.
Composition and morphology analysis are carried out to porous Si-C composite material manufactured in the present embodiment.It is its XRD as shown in Figure 1
Spectrum, Fig. 2 is the Raman collection of illustrative plates of the material, as can be seen that prepared material is Si-C composite material from collection of illustrative plates.Fig. 3 is many
The SEM figures of hole Si-C composite material.
The chemical property analysis of porous Si-C composite material lithium battery：
By porous Si-C composite material, conductive agent and adhesive are according to mass ratio 80:10:10 uniform mixing, and be coated with
Onto collector.Wherein conductive agent is carbon black (Super P), and adhesive is sodium carboxymethylcellulose (CMC).
The assembling of battery is carried out in the glove box full of argon gas.Wherein it is lithium electrode to electrode, electrolyte is 1M hexafluoros
Lithium phosphate (LiPF6) fluorinated ethylene carbonate (FEC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) (volume ratio 1:
1:1) solution, charging/discharging voltage scope is 0.01V-1.5V.Foregoing LiPF6, FEC, DMC, EMC can also use listed above
Other solutes and solvent are substituted.
Test condition：The load capacity of surveyed pole piece is 2mg/cm2, it is as shown in table 1 below, under the conditions of 500mA/g discharge and recharges
Test (preceding two circle is activated under 50mA/g current density), after multiple circulations, porous Si-C composite material is still protected
Good cyclical stability is held, charge specific capacity conservation rate is 81.5% (under the conditions of 500mA/g).Fig. 4 is that porous silicon-carbon is combined
The cycle performance figure of material.
The porous silica material of 1 embodiment of table 1 as negative active core-shell material cycle performance test result
Claims (10)
1. a kind of porous Si-C composite material, it is characterised in that it is composited by porous silicon and carbon material, carbon material cladding
On the surface of porous silicon, the particle diameter of described porous Si-C composite material is 1 μm -10 μm, and specific surface area is 10-30m2/g。
2. the preparation method of porous Si-C composite material as claimed in claim 1, it is characterised in that comprise the following steps：
1) mechanical ball mill and acid etch are carried out to ferro-silicium, obtaining silicone content in porous silica material, described ferro-silicium is
70wt%~80wt%, the content of metal impurities is 20wt%~30wt%, and described mechanical ball mill includes wet ball grinding or dry
Method ball milling, and the rotational speed of ball-mill used is 200r/min~500r/min, Ball-milling Time is 1h~64h, and ratio of grinding media to material is 1:1~
20:1；
2) porous silica material obtained by preparation and organic carbon source are mixed with suspension in deionized water, and will be mixed
Suspension carries out spraying pelletizing processing under spray dryer, obtained sample high temperature cabonization under an inert atmosphere again, is prepared into
To the porous Si-C composite material of final product.
3. the preparation method of porous Si-C composite material according to claim 2, it is characterised in that：Described organic carbon source
Including sucrose, glucose, citric acid or chitin, and described porous Si-C composite material and the quality of organic carbon source compare ratio
It is selected from the group：4:1,7:3,3:2,1:1,2:3.
4. the preparation method of porous Si-C composite material according to claim 2, it is characterised in that：Described inert atmosphere
Including argon gas, nitrogen, argon hydrogen gaseous mixture, described carburizing temperature is selected from the group：500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700
DEG C, 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C.
5. a kind of cell negative electrode material, it is characterised in that be that electricity is used as using porous Si-C composite material as claimed in claim 1
Pond negative active core-shell material.
6. cell negative electrode material as claimed in claim 5, it is characterised in that：Described porous Si-C composite material content is
60wt%~80wt%.
7. the cell negative electrode material as described in claim 5 or 6, it is characterised in that：Described cell negative electrode material is also included and led
Electric agent and/or adhesive.
8. cell negative electrode material as claimed in claim 7, it is characterised in that：10wt% is included in described cell negative electrode material
~20wt% conductive agents.
9. cell negative electrode material as claimed in claim 7, it is characterised in that：10wt% is included in described cell negative electrode material
~20wt% adhesives.
10. a kind of battery, it is characterised in that including positive electrode, negative material, electrolyte and barrier film, wherein, described negative pole
Material includes porous Si-C composite material as claimed in claim 1 or uses GND material as claimed in claim 5
Material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710356888.6A CN107275590A (en) | 2017-05-19 | 2017-05-19 | A kind of porous Si-C composite material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710356888.6A CN107275590A (en) | 2017-05-19 | 2017-05-19 | A kind of porous Si-C composite material and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107275590A true CN107275590A (en) | 2017-10-20 |
Family
ID=60065414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710356888.6A Pending CN107275590A (en) | 2017-05-19 | 2017-05-19 | A kind of porous Si-C composite material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107275590A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755483A (en) * | 2017-11-03 | 2019-05-14 | 北京万源工业有限公司 | A kind of preparation method and application of lithium ion battery silicon-carbon cathode material |
| CN109841803A (en) * | 2017-11-28 | 2019-06-04 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof and secondary battery containing material |
| CN110098380A (en) * | 2019-04-15 | 2019-08-06 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries |
| CN110289402A (en) * | 2019-06-10 | 2019-09-27 | 中国科学院合肥物质科学研究院 | It is crosslinked the electrode material and preparation method thereof of the mesoporous silicon particle of carbon coating |
| CN110854374A (en) * | 2019-11-26 | 2020-02-28 | 石家庄昭文新能源科技有限公司 | Porous carbon coated ferrosilicon alloy material and preparation method and application thereof |
| CN112289987A (en) * | 2020-09-30 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Organic-inorganic composite silicon-based negative electrode material and preparation method and application thereof |
| CN112366303A (en) * | 2020-11-16 | 2021-02-12 | 湖南上临新材料科技有限公司 | Nanocrystalline iron-silicon alloy-based negative electrode material for lithium ion battery and preparation method thereof |
| US20210102005A1 (en) * | 2019-10-02 | 2021-04-08 | University Of Louisiana At Lafayette | High-performance anodes for lithium ion batteries |
| CN112661131A (en) * | 2019-10-16 | 2021-04-16 | 中国科学院福建物质结构研究所 | Preparation method and application of carbon-coated silicon composite material |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104577045A (en) * | 2014-12-20 | 2015-04-29 | 江西正拓新能源科技股份有限公司 | Silicon-carbon composite material of lithium ion battery and preparation method of silicon-carbon composite material |
| CN105047892A (en) * | 2015-08-03 | 2015-11-11 | 中国科学院宁波材料技术与工程研究所 | Porous silicon material, and preparation method and application thereof |
| 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 |
| CN105226285A (en) * | 2014-06-19 | 2016-01-06 | 中国科学院宁波材料技术与工程研究所 | A kind of porous silicon carbon composite and preparation method thereof |
| CN105609711A (en) * | 2014-11-21 | 2016-05-25 | 国家纳米科学中心 | Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof |
-
2017
- 2017-05-19 CN CN201710356888.6A patent/CN107275590A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226285A (en) * | 2014-06-19 | 2016-01-06 | 中国科学院宁波材料技术与工程研究所 | A kind of porous silicon carbon composite and preparation method thereof |
| CN105609711A (en) * | 2014-11-21 | 2016-05-25 | 国家纳米科学中心 | Micro-nano structured silicon-carbon composite microsphere, preparation method and application thereof |
| CN104577045A (en) * | 2014-12-20 | 2015-04-29 | 江西正拓新能源科技股份有限公司 | Silicon-carbon composite material of lithium ion battery and preparation method of silicon-carbon composite material |
| 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 |
| CN105047892A (en) * | 2015-08-03 | 2015-11-11 | 中国科学院宁波材料技术与工程研究所 | Porous silicon material, and preparation method and application thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755483A (en) * | 2017-11-03 | 2019-05-14 | 北京万源工业有限公司 | A kind of preparation method and application of lithium ion battery silicon-carbon cathode material |
| CN109841803A (en) * | 2017-11-28 | 2019-06-04 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof and secondary battery containing material |
| CN109841803B (en) * | 2017-11-28 | 2021-12-07 | 宁德时代新能源科技股份有限公司 | Silicon-carbon composite material, preparation method thereof and secondary battery containing material |
| CN110098380A (en) * | 2019-04-15 | 2019-08-06 | 合肥国轩高科动力能源有限公司 | A kind of preparation method of Silicon Based Anode Materials for Lithium-Ion Batteries |
| CN110289402A (en) * | 2019-06-10 | 2019-09-27 | 中国科学院合肥物质科学研究院 | It is crosslinked the electrode material and preparation method thereof of the mesoporous silicon particle of carbon coating |
| CN110289402B (en) * | 2019-06-10 | 2022-09-16 | 中国科学院合肥物质科学研究院 | Electrode material of crosslinked carbon-coated mesoporous silicon particles and preparation method thereof |
| US20210102005A1 (en) * | 2019-10-02 | 2021-04-08 | University Of Louisiana At Lafayette | High-performance anodes for lithium ion batteries |
| US11926680B2 (en) * | 2019-10-02 | 2024-03-12 | University Of Louisiana At Lafayette | High-performance anodes for lithium ion batteries |
| CN112661131A (en) * | 2019-10-16 | 2021-04-16 | 中国科学院福建物质结构研究所 | Preparation method and application of carbon-coated silicon composite material |
| CN110854374A (en) * | 2019-11-26 | 2020-02-28 | 石家庄昭文新能源科技有限公司 | Porous carbon coated ferrosilicon alloy material and preparation method and application thereof |
| CN112289987A (en) * | 2020-09-30 | 2021-01-29 | 合肥国轩高科动力能源有限公司 | Organic-inorganic composite silicon-based negative electrode material and preparation method and application thereof |
| CN112366303A (en) * | 2020-11-16 | 2021-02-12 | 湖南上临新材料科技有限公司 | Nanocrystalline iron-silicon alloy-based negative electrode material for lithium ion battery and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107369825B (en) | Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof | |
| CN107275590A (en) | A kind of porous Si-C composite material and its preparation method and application | |
| CN105047892B (en) | Porous silica material, preparation method and application | |
| CN105226285B (en) | A kind of porous Si-C composite material and preparation method thereof | |
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN104934579B (en) | A kind of porous graphite doping and the preparation method of carbon coating graphite cathode material | |
| CN109148859B (en) | Preparation method of manganese oxide composite material coated by double carbon layers | |
| CN102916195B (en) | Graphene-coated copper oxide composite cathode material and method for manufacturing same | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN102244233B (en) | Method for preparing composite cathode material of graphene-like doped-cladded lithium titanate | |
| CN109767928B (en) | Synthetic method and application of fluorine-doped carbon-coated silicon oxide nanoparticle @ carbon nanotube composite material | |
| CN103151510A (en) | Lithium ion battery cathode material and preparation method thereof | |
| CN103151523B (en) | Preparation method of cuboid-shaped positive-pole FeF3(H2O)0.33 material | |
| CN102633300A (en) | Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof | |
| CN103390748B (en) | A kind of preparation method of alumina-coated lithium cobaltate cathode material | |
| CN105236486A (en) | High-performance lithium ion batteries cathode material vanadic pentoxide hollow microballoon and preparation method | |
| CN103606672A (en) | Rod-shaped nano iron oxide electrode material, and preparation method and application thereof | |
| CN104409712A (en) | Preparation method of carbon and nitrogen coated lithium titanate material | |
| CN108807912B (en) | C @ SnOx(x=0,1,2)Preparation and application of @ C mesoporous nano hollow sphere structure | |
| WO2017008615A1 (en) | Method for fabricating modified-silicon-based negative-electrode material by vapor deposition | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN106960947A (en) | Composite, its preparation method and application | |
| CN105185978A (en) | Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof | |
| CN102157727B (en) | Preparation method for nano MnO of negative electrode material of lithium ion battery | |
| CN111180704A (en) | Sodium-ion battery positive electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171020 |