CN105047892B - Porous silica material, preparation method and application - Google Patents
Porous silica material, preparation method and application Download PDFInfo
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- CN105047892B CN105047892B CN201510468107.3A CN201510468107A CN105047892B CN 105047892 B CN105047892 B CN 105047892B CN 201510468107 A CN201510468107 A CN 201510468107A CN 105047892 B CN105047892 B CN 105047892B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- 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 silica materials and its preparation method and application.The porous silica material mainly prepares gained using metallurgy with ferro-silicium as raw material by mechanical ball mill and acid etch, its size is micron/submicron rank, with diamond lattic structure, belong to Fd 3m (227) space group, and with the reaction phase that can be reacted with lithium (Li), and surface and inside further average and are furnished with a large amount of various sizes of classification pore passage structures.The porous silica material can be used as lithium ion battery anode active material, and its be applied to lithium ion battery when, the features such as showing high (for the first time) coulombic efficiency, high power capacity and superior cyclical stability, while its preparation process is simple, only needs conventional equipment that can implement, it is raw materials used cheap and easy to get, technical process is easily controllable, and reproducibility is good, and yield is high, product quality is stablized, and large-scale production is suitble to.
Description
Technical field
The present invention is more particularly directed to a kind of porous silica materials and its preparation method and application, such as porous as high coulombic efficiency
The purposes of silicium cathode active material and/or its application in battery, especially lithium ion battery, belong to materials science field.
Background technology
Environmental pollution and climate change are 21 century a great problems, and in order to solve this problem, national governments all put into
Prodigious energy develops New Energy Industry, such as：Solar energy, wind energy, tide energy etc..Lithium ion battery is as a kind of reliable
Energy storage means, since the advent of the world are exactly the hot spot studied.Currently, the lithium ion battery negative material of commercialization is using carbon
Material, have many advantages, such as that cycle efficieny is high, have extended cycle life, electrode potential it is relatively low.With in new-energy automobile, the wind energy sun
Can energy storage, intelligent grid energy storage with convert etc. fields huge applications market it is gradually clear, power lithium-ion battery by
Unprecedented concern.There are many deficiencies in power lithium-ion battery for graphite negative electrodes material, cannot meet high power lithium electricity
The demand in pond.
An important factor for lithium ion battery negative material is as the energy content of battery and cycle life is improved, is naturally ground
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, has lower
Removal lithium embedded current potential (<0.5V vs.Li/Li+) the advantages that, therefore once propose just by the extensive concern of researcher and become grind
Study carefully hot spot, is expected to become next-generation lithium ion battery negative material.However, researcher has found silicon based anode material in removal lithium embedded mistake
Serious volume change (volume expansion is more than 300%) occurs for Cheng Zhonghui, and electrode dusting, peeling etc. are caused due to volume change
Problem causes performance drastically to decline, poor circulation.Meanwhile the coulombic efficiency for the first time of silicon based anode material is relatively low, silicon is intrinsic
Conductivity is low, and the SEM of formation is unstable to be easy to fall off.These disadvantages limit its practical application in lithium ion battery.Separately
Outside, the preparation process for preparing high-performance silicon-based negative material is more complex also higher with manufacturing cost.
Therefore, a kind of height of coulombic efficiency for the first time is urgently developed in this field, and theoretical capacity is high, at low cost, cyclical stability
Good negative material.
Invention content
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of porous silica materials, have (first
It is secondary) the features such as coulombic efficiency is high, theoretical specific capacity is high, circulating battery stability is good.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
A kind of porous silica material is provided among some embodiments of the present invention, is mainly with metallurgical ferro-silicium
Raw material are prepared and to be formed by mechanical ball mill and acid etch.
Further, the porous silica material has diamond lattic structure, belongs to Fd-3m (227) space group, and with can be with
The reaction phase of lithium (Li) reaction.
Further, the size of the porous silica material is micron/submicron rank, and the surface of the porous silica material
Large number of orifices road is distributed with inside.
Further, the pattern of the porous silica material is irregular graininess.
Further, the grain size of the porous silica material is 0.1 μm~10 μm, preferably 0.5 μm~5 μm.
Further, the porous silica material specific surface area ranging from 0.5-50m2/ g is more preferably 5-25m2/g。
Further, the particle surface of the porous silica material and the internal duct that a large amount of hierarchical structures are distributed with.
It is another object of the present invention to provide a kind of methods preparing the porous silica material.
Among some embodiments, the preparation method of the porous silica material includes：
After carrying out mechanical ball mill processing to metallurgical ferro-silicium, then acid etch processing is carried out, to obtain the porous silicon
Material.
A further object of the present invention is to provide the porous silica material in preparing the purposes in chemical energy storage device.
Wherein, the chemical energy storage device includes but not limited to battery.
It is yet a further object of the present invention to provide a kind of cell negative electrode materials, and it includes the institutes as negative electrode active material
State porous silica material.
Further, the negative material also may include conductive agent and/or adhesive etc..
It is yet a further object of the present invention to provide a kind of batteries comprising positive electrode, negative material, electrolyte and every
Film, wherein the negative material includes the porous silica material or the electrode anode material.
It is yet a further object of the present invention to provide a kind of devices, and it includes the porous silica material, the batteries
Negative material or the battery.
Compared with prior art, advantages of the present invention includes at least：
(1) present invention is successfully prepared a kind of porous silica material being applicable as battery cathode active material, direct
Using when (without post-processings such as carbon coatings), show coulombic efficiency for the first time it is high (>88%), theoretical specific capacity it is high (>
1500mAh/g), the features such as circulating battery stability is good, same type of material far superior in the prior art；
(2) porous silica material preparation process provided by the invention is simple, only needs conventional equipment that can implement, and raw materials used
Cheap and easy to get, technical process is easily controllable, and reproducibility is good, and yield is high, and product quality is stablized, and is suitble to large-scale production.
More detailed explanation will hereafter be made to technical scheme of the present invention.It is understood, however, that in model of the present invention
In enclosing, above-mentioned each technical characteristic of the invention and specifically described in below (e.g. embodiment) can between each technical characteristic
It is combined with each other, to form a new or preferred technical solution.Due to space limitations, I will not repeat them here.
Description of the drawings
Fig. 1 is the XRD diagram of porous silica material prepared in the embodiment of the present invention 1；
Fig. 2 is the graph of pore diameter distribution of porous silica material inner duct prepared in the embodiment of the present invention 1；
Fig. 3 is the SEM figures of porous silica material prepared in the embodiment of the present invention 1；
Fig. 4 is the TEM figures of porous silica material prepared in the embodiment of the present invention 1；
Fig. 5 is the cycle performance curve graph of the electrode based on the porous silica material in the embodiment of the present invention 1；
Fig. 6 is the high rate performance curve graph of the electrode based on the porous silica material in the embodiment of the present invention 1；
Fig. 7 is the cycle performance curve graph of the electrode based on the porous silica material in the embodiment of the present invention 2；
Fig. 8 is the cycle performance curve graph of the electrode based on the porous silica material in the embodiment of the present invention 3；
Fig. 9 is the cycle performance curve graph of the electrode based on the porous silica material in the embodiment of the present invention 4；
Figure 10 is the cycle performance curve graph of the electrode based on the porous silica material in the embodiment of the present invention 5；
Figure 11 is the cycle performance curve graph of the electrode based on porous silica material in reference examples.
Specific implementation mode
As previously mentioned, in view of many deficiencies of the prior art, inventor's in-depth study and a large amount of by long-term
Practice is able to propose technical scheme of the present invention, as detailed below.
Porous silicon negative electrode active material
The first aspect of the present invention provides a kind of porous silica material (also referred to as porous silicon negative electrode active material as follows),
It is mainly prepared using metallurgical ferro-silicium as raw material.
Further, the porous silica material is mainly that raw material pass through mechanical ball mill and acid by metallurgical ferro-silicium
Etching is prepared.
Further, the size of the porous silica material is micron/submicron rank, and particle surface is distributed with greatly with inside
It takes measurements different ducts.
Further, the porous silica material has the reaction phase that can be reacted with lithium (Li).
Further, the porous silica material has diamond lattic structure.
Further, the porous silica material belongs to Fd-3m (227) space group.
Further, the pattern of the porous silica material is irregular graininess.
Further, the particle size range of the porous silica material is 0.1-10 μm, is more preferably 0.5-5 μm.
Further, the specific surface area of the porous silica material is 0.5-50m2/ g, further preferably 5-25m2/g。
It is more preferred, the particle surface of the porous silica material and the internal duct that a large amount of hierarchical structures are distributed with.
Specifically, micropore accounting 10%-40% in the duct of the hierarchical structure, mesoporous accounting 20%-30%, macropore
Accounting 30%-70%.
Wherein, micropore, mesoporous, macropore definition are identical as the definition of International Association for Pure and Applied Chemistry (IUPAC),
That is, micropore size is less than 2nm, macropore diameter is more than 50nm, and mesoporous (or mesoporous) aperture is 2 between 50nm.
Ferro-silicium material is set to be strained by Mechanical Milling Process in the present invention, defect and micro-structure are led to simultaneously
Cross acid etch formed porous structure, especially multilevel hierarchy duct, can effectively improve porous silicon negative material cycle performance with
And huge volume expansion problem during alloying with silicon is effectively relieved.
The preparation method of porous silicon negative electrode active material
The porous silicon negative electrode active material preparation method for material includes：Sonochemical method, wet chemical method, mechanico-chemical reaction
(such as mechanical alloying method and mechanical attrition method) etc..
Among a preferred embodiment, a kind of preparation method of porous silicon negative electrode active material includes：With metallurgy iron silicon
Alloy is raw material, is prepared by mechanical ball mill and acid etch and target product is made.
Among one more specifically embodiment, the preparation method may include steps of：
(i) the metallurgy iron silicon materials of silicon source are provided；
(ii) ferro-silicium is subjected to ball milling；
(iii) metal that ferro-silicium is carried out in acid etch reagent assists acid etch, and porous silica material is made.
In a preferred example, the mass percent of silicon is 1-99%, the quality of metal impurities in the metallurgical ferro-silicium
Percentage 1-99%；With the total weight of the metallurgical ferro-silicium.
In another preferred example, the mass percent of silicon is 20-99wt% in the metallurgical ferro-silicium, metal impurities
Mass percent is 1-80wt%；With the total weight of the metallurgical ferro-silicium.
In another preferred example, the mass percent of silicon is 50-90wt% in the metallurgical ferro-silicium, metal impurities
Mass percent is 10-50wt%；With the total weight of the metallurgical ferro-silicium.
In another preferred example, the mass percent of silicon is 70-80wt% in the metallurgical ferro-silicium, metal impurities
Mass percent is 20-30wt%；With the total weight of the metallurgical ferro-silicium.
In another preferred example, in the metallurgical ferro-silicium, the mass percentage of silicon is about 70-80wt%, with
The total weight of the alloy.
In another preferred example, the preparation method includes：Dry ball milling and/or wet ball grinding, acid etch.
Further, wet ball grinding is particularly preferably used in the preparation method, wherein because of the addition of solvent so that iron silicon
Alloying pellet is easily adhered on abrading-ball, to allow the energy of abrading-ball to be fully transmitted on ferro-silicium particle, Er Qierong
Agent can also reduce the surface energy of ferro-silicium particle, limit the reunion of ferro-silicium particle, promote the refinement of ferro-silicium particle.
In another preferred example, the milling atmosphere is selected from the group：Air, argon gas, nitrogen, ammonia, argon hydrogen gaseous mixture.
In another preferred example, the mechanical ball mill rotating speed is 200r/min~500r/min, especially preferably under
Group：200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min.
In another preferred example, the mechanical ball mill time is 1h~64h, especially preferably from the following group：1h, 2h, 4h,
8h, 12h, for 24 hours, 36h, 48h, 64h.
In another preferred example, the ratio of grinding media to material (abrading-ball：Raw material, mass ratio) it is 1:1~20:1, especially preferably
From the following group：1:1,2:1,3:Isosorbide-5-Nitrae:1,5:1,6:1,8:1,12:1,16:1,20:1.
In another preferred example, the solvent can be selected from the following group：Deionized water, absolute ethyl alcohol, ethylene glycol, acetone or its
Combination.
In another preferred example, the solvent material ratio is 1:5~5:1, especially preferably from the following group：1:5,1:4,1:
3,1:2,1:1,2:1,3:Isosorbide-5-Nitrae:1,5:1.
In the porous silica material preparation process of the present invention, by carrying out mechanical ball mill processing to ferro-silicium particle, it can make
Ferro-silicium obtains high-energy in mechanical milling process from the external world, to be strained in the middle introducing of material, defect and micro-structure, into
And the performance of material is caused to change.
It further says, changes in material properties above-mentioned, is primarily referred to as the ferro-silicium particle and particle surface has occurred
The variation of structure, crystal structure, physicochemical properties and mechanical chemical properties etc., and it is without being limited thereto.
It further says, grain surface texture variation above-mentioned is primarily referred to as the ferro-silicium particle in ball milling mistake
Violent collision and grinding occur because of the effect of mechanical force for Cheng Zhong, and particle size constantly reduces, the continuous shape of new surface defect
At specific surface area increases, particle surface chemical bond rupture, surface texture partial amorphism.
It further says, changes in crystal structure above-mentioned, is primarily referred to as the ferro-silicium particle in strong machinery
The defects of under force effect, particle refines, lattice generation dislocation, twin, grain boundary structure also changes.
It further says, physicochemical properties variation above-mentioned is primarily referred to as the ferro-silicium particle strong
Under mechanical force, the specific surface area and crystal structure of particle vary widely, and corresponding physicochemical properties also occur
Apparent variation, surface energy and electric conductivity are significantly improved.
It further says, mechanical chemical properties variation above-mentioned is primarily referred to as the ferro-silicium particle strong
Under mechanical force, the chemical composition of particle changes, and solid solution reaction, the conversion etc. of redox reaction and crystal form occurs.
In another preferred example, the acid etch is selected from the group with reagent：Dilute hydrochloric acid, dust technology, dilute sulfuric acid, hydrofluoric acid
Or combinations thereof.
In another preferred example, the sour processing method is selected from the group：It stands, stirring, be ultrasonically treated or combinations thereof.
In another preferred example, the sour processing time is 1h~48h, especially preferably from the following group：1h, 2h, 5h,
8h, 12h, 18h, 36h, 48h.
Also, among one more specifically case study on implementation, it is a kind of to prepare porous silica material by raw material of ferro-silicium
Method specifically includes following steps：
(i) it weighs a certain amount of industrial ferro-silicium and is put into ball grinder, solvent is added, finally weighs a certain amount of abrading-ball,
The mass ratio of abrading-ball and ferro-silicium is set as 8：1；
(ii) with the above-mentioned sample of the rotating speed ball milling of 300r/min 24 hours under air atmosphere；
(iii) the fine grained silicon alloy that ball milling obtains is subjected to pickling 12h with the hydrochloric acid solution of 2M；Then with 10% hydrogen
Oxide layer 6h existing for hydrofluoric acid cleaning surface；
(iv) material after etching is filtered through row, porous silica material is made in cleaning.
Wherein, the ferro-silicium can be bought by commercially available approach.
Wherein, the material of the ball grinder and abrading-ball is preferably from the following group：Stainless steel, agate, zirconium oxide etc..
Wherein, the porous silica material described in step (iv) can pass through water or the multiple filtering and washing of ethyl alcohol.
In the preparation process of the present invention, make the performance of material by carrying out mechanical ball mill processing to ferro-silicium particle first
It changes, later again by acid etch, forms the porous silica material with special appearance and structure, which exists
When using negative electrode active material for lithium ion battery, it is steady to show high (for the first time) coulombic efficiency, high power capacity and superior cycle
The features such as qualitative.Especially exceed that inventor is unexpected to be, even if porous silica material of the invention is in not carbon coated
In the case of also very high (close to 90%), and circulating battery efficiency still keeps stable to coulombic efficiency for the first time, this performance is significantly better than
The same type of material that document is reported.
Battery containing negative electrode active material
The porous silicon negative electrode active material of the present invention can be applied to chemical energy storage device, such as field of batteries.
Among an embodiment, a kind of product contains the porous silica material or the product by the porous silicon
Material is made.
In another preferred example, the product includes lithium ion battery or cell negative electrode material.
Among an embodiment, a kind of battery cathode active material includes the porous silica material or by described more
Hole silicon materials are made.
Among an embodiment, a kind of negative material includes the porous silica material as negative electrode active material.
In another preferred example, the negative material further includes conductive agent and/or adhesive.
In another preferred example, among the negative material, the content of the porous silica material is 60-80wt%.
In another preferred example, the content of the conductive agent is 10-20wt%.
In another preferred example, the content of the adhesive is 10-20wt%, with the total weight of negative material.
In another preferred example, in the negative material, the porous silica material, conductive agent, adhesive three's
Mass ratio is (70 ± 10):(10±2):(20±2).
Among an embodiment, a kind of battery includes positive electrode, negative material, electrolyte and diaphragm, and the cathode
Material includes the porous silica material as negative electrode active material.
Among an embodiment, the negative material is mainly by the porous silica material, conductive agent and adhesive composition.
More preferred, among the negative material, the content of porous silica material is 60-90wt%, and conductive agent contains
Amount is 10-20%, and the content of adhesive is 10-20wt%.
Wherein, the adhesive includes the polymeric derivative with carboxyl, but not limited to this.
In another preferred example, the battery also has shell.
The material of the shell is not particularly limited, and can be metal material, non-metal inorganic material, organic material or
Other composite materials etc..
In another preferred example, the battery is preferably non-aqueous battery.
Further, the diaphragm can be any one existing battery diaphragm of this field, as polytetrafluoroethylene (PTFE) every
Film, ceramic porous membrane, fibreglass diaphragm etc., and it is without being limited thereto.
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 preferred example, the electrolytic salt includes cation, and lithium salts can be used for example.Preferred lithium salts packet
Lithium hexafluoro phosphate, lithium perchlorate, lithium chloride, lithium bromide etc. are included, but not limited to this.
In another preferred example, the battery is lithium battery, and the electrolytic salt is selected from lithium salts, but not limited to this.
In another preferred example, 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.
In another preferred example, it is the preferred solvents organic solvent, 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 preferred example, the organic solvent includes at least one ring-type replaced by one or more halogen atoms
Carbonic acid ester derivative, such as the amyl- 2- ketone of fluoro- 1, the 3- dioxanes of 4-, but not limited to this, the cyclicity of electrode can be improved
Energy.
The electrolyte solvent can be used alone, and can also include two kinds or multi-solvents, electrolytic salt can be single
It solely uses, also may include two kinds or a variety of lithium salts.
Postscript, inventor have found through many experiments, when with the porous silica material of the present invention directly as negative electrode active
When material and various electrolyte above-mentioned, especially various lithium-ion battery electrolytes cooperations, coulombic efficiency for the first time is shown
The features such as (close to 90%), high charge-discharge specific capacity and circulating battery stabilised efficiency, shows the porous silica material tool of the present invention
There is quite good universality.
The positive electrode is not particularly limited, and can be selected with reference to state of the art, or using this
The existing positive electrode in field.
In a preferred example, the positive electrode includes one or more reactive metal oxides as positive-active
Material, and further include inactive metal element selected from the group below in the reactive metal oxides：Manganese (Mn), iron (Fe), cobalt
(Co), vanadium (V), nickel (Ni), chromium (Cr), or combinations thereof, and it is without being limited thereto.
Preferably, the positive electrode further includes component selected from the group below：Metal oxide, the metal of inactive metal
Sulfide, transition metal oxide, transient metal sulfide, or combinations thereof, and it is without being limited thereto.
In another preferred example, active metal above-mentioned is lithium.
In another preferred example, when the battery is lithium battery, the positive electrode further includes selected from the group below
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 combinations thereof.
Wherein, the transition metal oxide preferably certainly but is not limited to MnO2、V2O5Deng.
Wherein, the transient metal sulfide preferably certainly but is not limited to FeS2、MoS2、TiS2Deng.
Wherein, lithium ion transition metal oxide has obtained more applications, more preferably, can be selected from LiMn2O4,
LiCoO2, LiNi0.8Co0.15Al0.05O2, LiFePO4And LiNi0.33Mn0.33Co0.33O2In it is one or more and without being limited thereto.
Below in conjunction with specific embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition,
Or according to the normal condition proposed by manufacturer.Postscript, unless otherwise stated, otherwise following percentage and number are calculated by weight.
The preparation of 1 porous silicon negative electrode active material of embodiment (i.e. " porous silica material ")：
1) 2g metallurgy ferro-siliciums, 2g absolute ethyl alcohols and 16g agate abrading-balls are weighed, 100ml agate jars are added separately to.
2) ball grinder is put into ball mill, sets ball milling parameter, rotating speed 300r/min, the working time for 24 hours, often works
20min rests 10min.
3) the good form of small iron particles silicon alloy of ball milling filtered, washing, dried.
4) hydrochloric acid solution for measuring 100ml 2M is put into the beaker of 200ml, is slowly added to form of small iron particles silicon alloy, not
Disconnected stirring is finished until being added.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.Beaker is removed to be placed on magnetic stirring apparatus
It continuously stirs for 24 hours.It filters, drying.
5) it will be added in 10% hydrofluoric acid solution by the sample of HCl treatment, lasting stirring is for 24 hours.Filter, wash,
Porous silica material is made in drying.
Crystalline phase, pore-size distribution and morphology analysis are carried out to porous silicon negative electrode active material manufactured in the present embodiment.Such as Fig. 1 institutes
It is shown as its XRD spectrum, as can be seen that prepared porous silicon is pure phase silicon materials from the collection of illustrative plates.Fig. 2 is porous silica material
Graph of pore diameter distribution, even aperture distribution illustrate that a kind of hierarchical structure is presented in the duct of material.Fig. 3, Fig. 4 distinguish porous silica material
SEM photograph and TEM photos, can be seen that from Fig. 3, Fig. 4 and prepare the porous silica material of gained unique pore passage structure is presented,
Grain size scale is 1~2 μm.
The chemical property of porous silicon negative electrode active material lithium battery is analyzed：
By porous silica material, conductive agent and adhesive proportionally 70:10:20 uniformly mixing, and be applied on carrying object.
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.It is wherein 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 ranging from 0.01V-1.5V.LiPF above-mentioned6, FEC, DMC, EMC can also use it is listed above
Other solutes and solvent substitute.
Test condition：The load capacity of surveyed pole piece is 1.5mg/cm2, respectively in 50mA/g, 100mA/g, 200mA/g,
It is tested under the current conditions such as 500mA/g, 1000mA/g, 2000mA/g, 5000mA/g, 10000mA/g.As shown in table 1 below, exist
Test (preceding two circle is activated under the current density of 50mA/g), more after multiple cycles under the conditions of 500mA/g charge and discharge
It is 81.5% (under the conditions of 500mA/g) that hole silicon materials, which still keep good cyclical stability, charge specific capacity conservation rate,.Fig. 5, figure
6 be the cycle performance figure and high rate performance figure of porous silicon negative material respectively.In the high rate performance figure of Fig. 6, in 5000mA/g
Current density under, the reversible capacity of the material still up to 550mAh/g, show hierarchical structure duct have it is good
Electronics and ion transmission performance.
Cycle performance test result of 1 embodiment of table, 1 porous silica material as negative electrode active material
The preparation of 2 porous silicon negative electrode active material of embodiment：
1) it weighs and weighs 2g metallurgy ferro-siliciums in argon atmosphere respectively, 1g absolute ethyl alcohols and 8g agate abrading-balls add respectively
Enter to 100ml agate jars.
2) ball grinder is put into ball mill, sets ball milling parameter, rotating speed 400r/min, working time 12h often work
10min rests 10min.
3) the good form of small iron particles silicon alloy of ball milling filtered, washing, dried.
4) hydrofluoric acid solution for measuring 100ml 10% is put into the plastic beaker of 200ml, is slowly added to form of small iron particles silicon
Alloy, and be stirred continuously and finished until being added.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.It removes beaker and is placed on magnetic
12h is continuously stirred on power blender.It filters, washing, dry, porous silica material is made.
It is tested according to mode similar to Example 1 porous silica material obtained to the present embodiment, cycle performance test
The results are shown in Figure 7.
The preparation of 3 porous silicon negative electrode active material of embodiment：
1) it weighs and weighs 2g metallurgy ferro-siliciums, 0.4g absolute ethyl alcohols and 2g zirconia balls in argon atmosphere respectively, respectively
It is added to 100ml zirconia ball grinding jars.
2) ball grinder is put into ball mill, sets ball milling parameter, rotating speed 200r/min, working time 64h often work
20min rests 10min.
3) the good form of small iron particles silicon alloy of ball milling filtered, washing, dried.
4) hydrofluoric acid solution for measuring 100ml 10% is put into the plastic beaker of 200ml, is slowly added to form of small iron particles silicon
Alloy, and be stirred continuously and finished until being added.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.It removes beaker and is placed on magnetic
1h is continuously stirred on power blender.It filters, washing, dry, porous silica material is made.
It is tested according to mode similar to Example 1 porous silica material obtained to the present embodiment, cycle performance test
The results are shown in Figure 8.
The preparation of 4 porous silicon negative electrode active material of embodiment：
1) it weighs and weighs 2g metallurgy ferro-siliciums, 10g absolute ethyl alcohols and 40g steel balls in argon atmosphere respectively, be separately added into
To 200ml steel ball grinders.
2) ball grinder is put into ball mill, sets ball milling parameter, rotating speed 500r/min, working time 1h, often work 10min
Rest 10min.
3) the good form of small iron particles silicon alloy of ball milling filtered, washing, dried.
4) hydrofluoric acid solution for measuring 100ml 10% is put into the plastic beaker of 200ml, is slowly added to form of small iron particles silicon
Alloy, and be stirred continuously and finished until being added.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.It removes beaker and is placed on magnetic
48h is continuously stirred on power blender.It filters, washing, dry, porous silica material is made.
It is tested according to mode similar to Example 1 porous silica material obtained to the present embodiment, wherein electrolyte is changed to
Ethylene carbonate (Ethylene Carbonate), dimethyl carbonate (DMC) and the methyl ethyl carbonate of 1M lithium hexafluoro phosphates (LiPF6)
Ester (EMC) (volume ratio 1:1:1) solution.Test results are shown in figure 9 for its cycle performance.
The preparation of 5 porous silicon negative electrode active material of embodiment：
1) 2g metallurgy ferro-silicium and 8g agate abrading-balls are weighed under air conditions, are added separately to 100ml agate ball millings
Tank.
2) ball grinder is put into ball mill, sets ball milling parameter, rotating speed 300r/min, the working time for 24 hours, often works
20min rests 10min.
3) by the good form of small iron particles silicon alloy washing of ball milling, drying.
4) hydrofluoric acid solution for measuring 100ml 5% is put into the plastic beaker of 200ml, is slowly added to the conjunction of form of small iron particles silicon
Gold, and be stirred continuously and finished until being added.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.It removes beaker and is placed on magnetic force
5h is continuously stirred on blender.It filters, washing, dry, porous silica material is made.
It is tested according to mode similar to Example 1 porous silica material obtained to the present embodiment, cycle performance test
The results are shown in Figure 10.
In addition, inventor is referring also to embodiment 1-3, and replace with other process conditions listed above, such as
Other a variety of rotational speed of ball-mill, Ball-milling Time, ratio of grinding media to material, solvent material ratio, the acid etch reagents of other types, other types
Sour processing time etc. has carried out the production of porous silica material, and with reference to the mode of embodiment 1 to pattern, the performance etc. of obtained product
It is tested, it is found that its (for the first time) coulombic efficiency, capacity and cyclical stability etc. are approximate with 1 product of embodiment.
The preparation of reference examples porous silicon negative electrode active material：
1) 2g metallurgy ferro-siliciums are weighed, are crushed using the method that physics is cut, and be sieved, grain size point is obtained
The relatively uniform form of small iron particles silicon alloy of cloth, washing, drying.
2) hydrochloric acid solution for measuring 100ml 2M is put into the beaker of 200ml, is slowly added to form of small iron particles silicon alloy, not
Disconnected stirring is finished until being added.Beaker is put into ultrasonic disperse 30min in ultrasonic instrument.Beaker is removed to be placed on magnetic stirring apparatus
It continuously stirs for 24 hours.It filters, drying.
3) it will be added in 10% hydrofluoric acid solution by the sample of HCl treatment, lasting stirring is for 24 hours.Filter, wash,
Porous silica material is made in drying.
It is tested according to mode similar to Example 1 porous silica material obtained to this reference examples, cycle performance test
As a result as shown in Figure 11 and table 2, it can be seen that the charge-discharge performance of the porous silica material prepared without ball-milling treatment obviously compares
Present invention negative material chemical property prepared after ball-milling technology regulates and controls is poor, it was demonstrated that the present invention is by early period to iron silicon
Alloying pellet, which carries out mechanical ball mill processing, makes the performance of material be changed, and later again by acid etch, forms with spy
The porous silica material of different pattern and structure shows chemical property that is excellent, exceeding those skilled in the art's expectation.
Cycle performance test result of the 2 reference examples porous silica material of table as negative electrode active material
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for the skill of this field
For art personnel, the application can have various modifications and variations.Within the spirit and principles of this application, any made by repair
Change, equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (20)
1. a kind of porous silica material, which is characterized in that the preparation method of the porous silica material includes：
To metallurgical ferro-silicium carry out mechanical ball mill processing, it is described metallurgy ferro-silicium in silicone content be 70wt%~80wt%,
The content of metal impurities is 20wt%~30wt%, and the mechanical ball mill selects wet ball grinding or dry ball milling, and the ball used
Mill rotating speed is 200r/min~500r/min, and Ball-milling Time is 1h~64h, ratio of grinding media to material 1:1~20:1；
To through mechanical ball mill treated metallurgical ferro-silicium carries out metal assists acid etch in acid etch reagent, at acid etch
The time of reason is 1h~48h, and porous silica material is made；
Also, the porous silica material has diamond lattic structure, belong to Fd-3m (227) space group, and with can be reacted with lithium
Phase is reacted, meanwhile, the grain size of the porous silica material is 0.5 μm -5 μm, specific surface area 5-25m2/ g, particle surface and inside
It is distributed with the duct of hierarchical structure, micropore accounting 10%-40%, mesoporous accounting 20%-30% in the duct of the hierarchical structure,
Macropore accounting 30%-70%.
2. the preparation method of porous silica material as described in claim 1, it is characterised in that including：
To metallurgical ferro-silicium carry out mechanical ball mill processing, it is described metallurgy ferro-silicium in silicone content be 70wt%~80wt%,
The content of metal impurities is 20wt%~30wt%, and the mechanical ball mill selects wet ball grinding or dry ball milling, and the ball used
Mill rotating speed is 200r/min~500r/min, and Ball-milling Time is 1h~64h, ratio of grinding media to material 1:1~20:1；
To through mechanical ball mill treated metallurgical ferro-silicium carries out metal assists acid etch in acid etch reagent, at acid etch
The time of reason is 1h~48h, and porous silica material is made.
3. the preparation method of porous silica material according to claim 2, it is characterised in that：The ball milling gas of the mechanical ball mill
Atmosphere includes air, argon gas, nitrogen, ammonia or argon hydrogen mixed atmosphere.
4. the preparation method of porous silica material according to claim 2, it is characterised in that：The ball milling of the mechanical ball mill turns
Speed is selected from the group：200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min or 500r/min.
5. the preparation method of porous silica material according to claim 2, it is characterised in that：When the ball milling of the mechanical ball mill
Between be selected from the group：1h, 2h, 4h, 8h, 12h, for 24 hours, 36h, 48h or 64h.
6. the preparation method of porous silica material according to claim 2, it is characterised in that：It is used in the mechanical ball mill
Ratio of grinding media to material is selected from the group：1:1,2:1,3:Isosorbide-5-Nitrae:1,5:1,6:1,8:1,12:1,16:1 or 20:1.
7. the preparation method of porous silica material according to claim 2, it is characterised in that：It is used in the mechanical ball mill
Abrading-ball is selected from steel ball, agate ball, corundum ball, any one in tungsten-carbide ball and zirconia ball or two or more combinations.
8. the preparation method of porous silica material according to claim 2, it is characterised in that：The mechanical ball mill uses wet method
Ball milling, any one or two or more group of the solvent therein in deionized water, absolute ethyl alcohol, ethylene glycol and acetone
It closes.
9. the preparation method of porous silica material according to claim 2, it is characterised in that：The mechanical ball mill uses wet method
Ball milling, solvent material ratio therein are 1:5~5:1.
10. the preparation method of porous silica material according to claim 9, it is characterised in that：The solvent material ratio choosing
From the following group：1:5,1:4,1:3,1:2,1:1,2:1,3:Isosorbide-5-Nitrae:1 or 5:1.
11. the preparation method of porous silica material according to claim 2, it is characterised in that：The acid etch reagent is selected from
Dilute hydrochloric acid, dust technology, dilute sulfuric acid, any one in hydrofluoric acid or two or more combinations.
12. the preparation method of porous silica material according to claim 2, it is characterised in that：The side of the acid etch processing
Method, which is selected from, to be stood, stirring, any one in supersound process or two or more combinations.
13. the preparation method of porous silica material according to claim 11, it is characterised in that：Acid etch processing when
Between be selected from the group：1h, 2h, 5h, 8h, 12h, 18h, 36h or 48h.
14. a kind of cell negative electrode material, it is characterised in that it includes as negative electrode active material, as described in claim 1
Porous silica material.
15. cell negative electrode material as claimed in claim 14, it is characterised in that：The cell negative electrode material include 60wt%~
Porous silica material described in 80wt%.
16. the cell negative electrode material as described in claims 14 or 15, it is characterised in that：The cell negative electrode material also includes to lead
Electric agent and/or adhesive.
17. cell negative electrode material as claimed in claim 16, it is characterised in that：The cell negative electrode material include 10wt%~
20wt% conductive agents.
18. cell negative electrode material as claimed in claim 16, it is characterised in that：The cell negative electrode material include 10wt%~
20wt% adhesives.
19. cell negative electrode material as claimed in claim 17, it is characterised in that：The cell negative electrode material is comprising mass ratio
(70±10):(10±2):The porous silica material, conductive agent and the adhesive of (20 ± 2).
20. a kind of battery, including positive electrode, negative material, electrolyte and diaphragm, it is characterised in that the negative material includes
Cell negative electrode material described in any one of porous silica material described in claim 1 or claim 14-19.
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| CN105609740B (en) * | 2016-03-01 | 2019-08-16 | 北京壹金新能源科技有限公司 | A kind of silicon alloy complex microsphere and preparation method and application |
| WO2018034553A1 (en) | 2016-08-18 | 2018-02-22 | 주식회사 엘지화학 | Negative electrode material comprising silicon flakes and method for preparing silicon flakes |
| CN106684364B (en) * | 2017-01-26 | 2020-04-24 | 南京大学 | Nano porous material and preparation method thereof |
| CN106784743A (en) * | 2017-02-28 | 2017-05-31 | 山东泰纳新材料科技有限公司 | A kind of low thermal expansion porous silicon/graphite combination electrode material and preparation method thereof |
| CN107215874B (en) * | 2017-05-09 | 2020-03-10 | 武汉科技大学 | Preparation method of ant nest-shaped porous silicon for lithium ion battery |
| CN107140641B (en) * | 2017-05-09 | 2019-05-31 | 武汉科技大学 | A method of three-dimensional porous silicon is prepared by raw material of silicate glass |
| CN107275590A (en) * | 2017-05-19 | 2017-10-20 | 浙江大学 | A kind of porous Si-C composite material and its preparation method and application |
| CN107611416B (en) * | 2017-08-15 | 2020-07-07 | 武汉科技大学 | Silicon-carbon composite material, preparation method and application thereof |
| CN108011090B (en) * | 2017-12-03 | 2020-06-05 | 山西长韩新能源科技有限公司 | Method for preparing lithium ion battery cathode, battery cathode prepared by method and lithium ion battery |
| CN108493417A (en) * | 2018-03-22 | 2018-09-04 | 山东大学 | A kind of composite material and preparation method of gradient nano porous silicon metal |
| 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 |
| EP4131486A4 (en) * | 2020-03-31 | 2023-05-10 | Ningde Amperex Technology Limited | Negative electrode material, negative pole piece, electrochemical apparatus and electronic apparatus |
| CN113169324B (en) * | 2021-02-26 | 2022-05-17 | 上海杉杉科技有限公司 | Porous negative electrode active material and method for producing same |
| CN114988413B (en) * | 2022-05-05 | 2024-03-15 | 昆明理工大学 | Method for preparing high-purity porous silicon |
| CN115642292B (en) * | 2022-12-26 | 2023-06-09 | 中国科学院宁波材料技术与工程研究所 | Zero strain all-solid-state lithium aluminum battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518144A (en) * | 2003-01-06 | 2004-08-04 | ����Sdi��ʽ���� | Nagative active material for recharge lithium battery, its manufacturing method and recharge lithium battery |
| CN103165874A (en) * | 2013-04-10 | 2013-06-19 | 上海空间电源研究所 | Porous silicon negative material of lithium ion battery and preparation method and application of material |
-
2015
- 2015-08-03 CN CN201510468107.3A patent/CN105047892B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1518144A (en) * | 2003-01-06 | 2004-08-04 | ����Sdi��ʽ���� | Nagative active material for recharge lithium battery, its manufacturing method and recharge lithium battery |
| CN103165874A (en) * | 2013-04-10 | 2013-06-19 | 上海空间电源研究所 | Porous silicon negative material of lithium ion battery and preparation method and application of material |
Non-Patent Citations (1)
| Title |
|---|
| Large-Scale Fabrication，3D Tomography，and Lithium-Ion Battery Application of Porous Silicon;Mingyuan Ge等;《Nano Lett.》;20131126;第14卷;第261-268页 * |
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