CN105047892A - Porous silicon material, and preparation method and application thereof - Google Patents
Porous silicon material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN105047892A CN105047892A CN201510468107.3A CN201510468107A CN105047892A CN 105047892 A CN105047892 A CN 105047892A CN 201510468107 A CN201510468107 A CN 201510468107A CN 105047892 A CN105047892 A CN 105047892A
- Authority
- CN
- China
- Prior art keywords
- porous silica
- silica material
- ball
- porous silicon
- preferred
- 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.)
- Granted
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
- H01M4/38—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
- 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
-
- 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 porous silicon material, and a preparation method and an application thereof. The porous silicon material is mainly prepared by mechanical milling and acid etching of metallurgical iron-silicon alloy as a raw material; the dimension of the porous silicon material is in micron/submicron level; the porous silicon material has a diamond structure, belongs to an Fd-3m (227) space group, and has a reaction phase which can react with lithium (Li); a large number of hierarchical porous structures with different dimensions are evenly distributed in the surface and the inside of the porous silicon material; the porous silicon material can be used as a lithium ion battery anode active material, and shows the characteristics of high (first) coulombic efficiency, high capacity, excellent cycling stability and the like when applied to a lithium ion battery; meanwhile, the preparation technology of the porous silicon material is simple, and can be carried out only by conventional equipment; the used raw materials are cheap and available; the technological process is easy to control; and the porous silicon material is good in repeatability, high in productivity, stable in product quality and suitable for large-scale production.
Description
Technical field
The present invention be more particularly directed to a kind of porous silica material and its preparation method and application, such as high coulombic efficiency porous silicon negative active core-shell material purposes and/or it is at battery, the application particularly in lithium ion battery, belongs to material science.
Background technology
Environmental pollution and climate change are 21 century a great problems, and in order to address this problem, national governments have all dropped into very large energy development New Energy Industry, such as: solar energy, and wind energy, tidal energy etc.Lithium ion battery, as the reliable energy storage means of one, has been exactly the focus of research since coming out.At present, what commercial lithium ion battery negative material adopted is carbon materials, its have cycle efficieny high, have extended cycle life, the advantage such as electrode potential is lower.Along with progressively clear in huge applications markets, field such as new-energy automobile, wind and solar energy energy storage, intelligent grid energy storage and conversions, power lithium-ion battery receives unprecedented concern.There is many deficiencies in graphite negative electrodes material, can not meet the demand of high-power lithium battery in power lithium-ion battery.
Lithium ion battery negative material, as the key factor improving the energy content of battery and cycle life, is naturally subject to the favor of researcher.Compared with other negative materials, the lithium storage content of silicon based anode material, up to 3579mAh/g, has lower removal lithium embedded current potential (<0.5Vvs.Li/Li
+) etc. advantage, therefore once propose just be subject to researcher extensive concern and become study hotspot, be expected to become lithium ion battery negative material of future generation.But researcher finds that serious change in volume (volumetric expansion is more than 300%) can occur silicon based anode material in removal lithium embedded process, problem causes performance sharply to decline to cause electrode efflorescence due to change in volume, peel off etc., and cycle performance is poor.Meanwhile, the coulombic efficiency first of silicon based anode material is also lower, and silicon intrinsic conductivity is low, and the SEM instability of formation easily comes off.These shortcomings limit its practical application in lithium ion battery.In addition, the preparation technology preparing high-performance silicon-based negative material is more complicated also higher with preparation cost.
Therefore, one is urgently developed in this area, and coulombic efficiency is high first, and theoretical capacity is high, and cost is low, the negative material of good cycling stability.
Summary of the invention
For the deficiencies in the prior art, one object of the present invention is to provide a kind of porous silica material, and it has (first) coulombic efficiency is high, the feature such as theoretical specific capacity is high, circulating battery good stability.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
Among some embodiments of the present invention, provide a kind of porous silica material, its mainly with metallurgy iron silicon alloy for raw material prepare formation through mechanical ball milling and acid etch.
Further, described porous silica material has diamond lattic structure, belongs to Fd-3m (227) space group, and has the reacting phase that can react with lithium (Li).
Further, described porous silica material is of a size of micron/submicron rank, and the surface of described porous silica material and inside are distributed with a large amount of duct.
Further, the pattern of described porous silica material is irregular graininess.
Further, the particle diameter of described porous silica material is 0.1 μm ~ 10 μm, is preferably 0.5 μm ~ 5 μm.
Further, described porous silica material specific area scope is 0.5-50m
2/ g is more preferably 5-25m
2/ g.
Further, the particle surface of described porous silica material and the inner duct being distributed with a large amount of hierarchy.
Another object of the present invention is to provide a kind of method preparing described porous silica material.
Among some embodiments, the preparation method of described porous silica material comprises:
After mechanical ball-milling treatment is carried out to metallurgy iron silicon alloy, then carry out acid etch process, thus obtain described porous silica material.
Another object of the present invention is to provide the purposes of described porous silica material in preparative chemistry energy storage device.
Wherein, described chemical energy storage device includes but not limited to battery.
Another object of the present invention is to provide a kind of cell negative electrode material, and it comprises the described porous silica material as negative active core-shell material.
Further, described negative material also can comprise conductive agent and/or adhesive etc.
Another object of the present invention is to provide a kind of battery, and it comprises positive electrode, negative material, electrolyte and barrier film, and wherein, described negative material comprises described porous silica material or described electrode anode material.
Another object of the present invention is to provide a kind of device, and it comprises described porous silica material, described cell negative electrode material or described battery.
Compared with prior art, advantage of the present invention at least comprises:
(1) the present invention has successfully prepared a kind of porous silica material being applicable as battery cathode active material, it (does not carry out reprocessing such as carbon coated grade) when directly applying, show the features such as coulombic efficiency first high (>88%), theoretical specific capacity high (>1500mAh/g), circulating battery good stability, be far superior to same type of material of the prior art;
(2) porous silica material preparation technology provided by the invention is simple, only needs conventional equipment to implement, and raw materials used all cheap and easy to get, and technical process is easy to control, and reproducibility is good, and productive rate is high, constant product quality, is applicable to large-scale production.
Hereafter do more detailed explanation explanation by technical scheme of the present invention.But, should be appreciated that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is the XRD figure 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 figure of porous silica material prepared in the embodiment of the present invention 1;
Fig. 4 is the TEM figure of porous silica material prepared in the embodiment of the present invention 1;
Fig. 5 is the cycle performance curve chart based on the electrode of described porous silica material in the embodiment of the present invention 1;
Fig. 6 is the high rate performance curve chart based on the electrode of described porous silica material in the embodiment of the present invention 1;
Fig. 7 is the cycle performance curve chart based on the electrode of described porous silica material in the embodiment of the present invention 2;
Fig. 8 is the cycle performance curve chart based on the electrode of described porous silica material in the embodiment of the present invention 3;
Fig. 9 is the cycle performance curve chart based on the electrode of described porous silica material in the embodiment of the present invention 4;
Figure 10 is the cycle performance curve chart based on the electrode of described porous silica material in the embodiment of the present invention 5;
Figure 11 is the cycle performance curve chart based on the electrode of porous silica material in reference examples.
Embodiment
As previously mentioned, in view of many deficiencies of prior art, inventor, through long-term and deep research and a large amount of practice, is proposed technical scheme of the present invention, is referred to hereafter.
Porous silicon negative active core-shell material
A first aspect of the present invention provides a kind of porous silica material (also can be described as porous silicon negative active core-shell material as follows), its mainly with metallurgy iron silicon alloy for raw material are prepared from.
Further, mainly by metallurgy iron silicon alloy, to be raw material through mechanical ball milling and acid etch prepare described porous silica material obtains.
Further, described porous silica material is of a size of micron/submicron rank, and particle surface is distributed with from inside different duct of taking measurements greatly.
Further, described porous silica material has the reacting phase that can react with lithium (Li).
Further, described porous silica material has diamond lattic structure.
Further, described porous silica material belongs to Fd-3m (227) space group.
Further, the pattern of described porous silica material is irregular graininess.
Further, the particle size range of described porous silica material is 0.1-10 μm, is more preferably 0.5-5 μm.
Further, the specific area of described porous silica material is 0.5-50m
2/ g, more preferably 5-25m
2/ g.
Comparatively preferred, the particle surface of described porous silica material and the inner duct being distributed with a large amount of hierarchy.
Specifically, micropore accounting 10%-40% in the duct of described hierarchy, mesoporous accounting 20%-30%, macropore accounting 30%-70%.
Wherein, micropore, definition that is mesoporous, macropore are identical with the definition of IUPAC (IUPAC), that is, micropore size is less than 2nm, and macropore diameter is greater than 50nm, and mesoporous (or claiming mesopore), aperture was between 2 to 50nm.
Ferro-silicium material is made to obtain strain by Mechanical Milling Process in the present invention, defect and micro-structural, form loose structure by acid etch simultaneously, particularly multilevel hierarchy duct, effectively can improve porous silicon negative material cycle performance and effectively alleviate volumetric expansion problem huge in alloying with silicon process.
The preparation method of porous silicon negative active core-shell material
Described porous silicon negative electrode active material preparation method for material comprises: sonochemical method, wet chemical method, mechanico-chemical reaction (such as mechanical alloying method and mechanical attrition method) etc.
Among a better embodiment, a kind of preparation method of porous silicon negative active core-shell material comprises: with metallurgy iron silicon alloy for raw material, the obtained target product through mechanical ball milling and acid etch preparation.
Among one more specifically embodiment, described preparation method can comprise the steps:
I () provides the metallurgy iron silicon materials in silicon source;
(ii) described ferro-silicium is carried out ball milling;
(iii) in acid etch reagent, the metal auxiliary acid etching of ferro-silicium is carried out, obtained porous silica material.
In a preference, in described metallurgy iron silicon alloy, the mass percent of silicon is the mass percent 1-99% of 1-99%, metal impurities; With the total weight of described metallurgy iron silicon alloy.
In another preference, in described metallurgy iron silicon alloy, the mass percent of silicon is 20-99wt%, and the mass percent of metal impurities is 1-80wt%; With the total weight of described metallurgy iron silicon alloy.
In another preference, in described metallurgy iron silicon alloy, the mass percent of silicon is 50-90wt%, and the mass percent of metal impurities is 10-50wt%; With the total weight of described metallurgy iron silicon alloy.
In another preference, in described metallurgy iron silicon alloy, the mass percent of silicon is 70-80wt%, and the mass percent of metal impurities is 20-30wt%; With the total weight of described metallurgy iron silicon alloy.
In another preference, in described metallurgy iron silicon alloy, the mass percentage of silicon is about 70-80wt%, with the total weight of described alloy.
In another preference, described preparation method comprises: dry ball milling and/or wet ball grinding, acid etch.
Further, especially preferably wet ball grinding is adopted in described preparation method, adding wherein because of solvent, ferro-silicium particle is easily sticked on abrading-ball, thus the energy of abrading-ball can be fully delivered on ferro-silicium particle, and solvent can also reduce the surface energy of ferro-silicium particle, the reunion of restriction ferro-silicium particle, impels the refinement of ferro-silicium particle.
In another preference, described milling atmosphere is selected from lower group: air, argon gas, nitrogen, ammonia, argon hydrogen gaseous mixture.
In another preference, described mechanical rotational speed of ball-mill is 200r/min ~ 500r/min, especially can preferably from lower group: 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min.
In another preference, described mechanical ball time consuming is 1h ~ 64h, especially can preferably from lower group: 1h, 2h, 4h, 8h, 12h, 24h, 36h, 48h, 64h.
In another preference, described ratio of grinding media to material (abrading-ball: raw material, mass ratio) is 1:1 ~ 20:1, especially can preferably from lower group: 1:1,2:1,3:1,4:1,5:1,6:1,8:1,12:1,16:1,20:1.
In another preference, described solvent can be selected from lower group: deionized water, absolute ethyl alcohol, ethylene glycol, acetone or its combination.
In another preference, described solvent material ratio is 1:5 ~ 5:1, especially can preferably from lower group: 1:5,1:4,1:3,1:2,1:1,2:1,3:1,4:1,5:1.
In porous silica material preparation technology of the present invention, by carrying out mechanical ball-milling treatment to ferro-silicium particle, ferro-silicium can be made in mechanical milling process to obtain high-energy from the external world, thus introduce strain in material, defect and micro-structural, and then cause the performance of material to change.
Further say, aforesaid changes in material properties, mainly refer to that described ferro-silicium particle there occurs grain surface texture, crystal structure, the change of the aspect such as physicochemical properties and mechanical chemical properties, and be not limited thereto.
Further say, aforesaid grain surface texture change, mainly refer to that described ferro-silicium particle is in mechanical milling process, violent collision and grinding is there is because of the effect of mechanical force, particle size constantly reduces, and new blemish is constantly formed, and specific area increases, particle surface chemical bond rupture, surface texture partial amorphism.
Further say, aforesaid changes in crystal structure, mainly refer to that described ferro-silicium particle is under strong mechanical force, grain refine, lattice produces dislocation, and the defects such as twin, grain boundary structure also changes.
Further say, aforesaid physicochemical properties change, mainly refer to that described ferro-silicium particle is under strong mechanical force, there is larger change in the specific area of particle and crystal structure, corresponding physicochemical properties also there occurs obvious change, and surface energy and electric conductivity are significantly improved.
Further say, aforesaid mechanical chemical properties change, mainly refer to that described ferro-silicium particle is under strong mechanical force, the chemical composition of particle changes, and solid solution reaction occurs, the conversion etc. of redox reaction and crystal formation.
In another preference, described acid etch reagent is selected from lower group: watery hydrochloric acid, dust technology, dilute sulfuric acid, hydrofluoric acid or its combination.
In another preference, described acid treatment method is selected from lower group: leave standstill, and stirs, ultrasonic process or its combination.
In another preference, the described acid treatment time is 1h ~ 48h, especially can preferably from lower group: 1h, 2h, 5h, 8h, 12h, 18h, 36h, 48h.
Again, among one more specifically case study on implementation, a kind of method with ferro-silicium being porous silica material prepared by raw material specifically comprises the following steps:
I () takes a certain amount of industrial ferro-silicium and puts into ball grinder, add solvent, finally takes a certain amount of abrading-ball, and the mass ratio of abrading-ball and ferro-silicium is set as 8:1;
(ii) under air atmosphere with the above-mentioned sample of the rotating speed ball milling of 300r/min 24 hours;
(iii) hydrochloric acid solution of the fine particle silicon alloy 2M obtained by ball milling carries out pickling 12h; Then with 10% hydrofluoric acid clean surface exist oxide layer 6h;
(iv) by the material after etching through row suction filtration, cleaning, obtained porous silica material.
Wherein, described ferro-silicium can be bought by commercially available approach.
Wherein, the material of described ball grinder and abrading-ball can preferably from lower group: stainless steel, agate, zirconia etc.
Wherein, the porous silica material described in step (iv) can pass through water or ethanol repeatedly filtering and washing.
In preparation technology of the present invention, first by carrying out mechanical ball-milling treatment to ferro-silicium particle, the performance of material is changed, pass through acid etch more afterwards, define the porous silica material with special appearance and structure, this porous silica material, when being applied as the negative active core-shell material of lithium ion battery, shows the features such as height (first) coulombic efficiency, high power capacity and superior cyclical stability.Especially exceed that inventor is unexpected is, even if coulombic efficiency is also very high (close to 90%) first when not carbon coated for porous silica material of the present invention, and circulating battery efficiency still keeps stable, this performance is significantly better than the same type of material that document is reported.
Battery containing negative active core-shell material
Porous silicon negative active core-shell material of the present invention can be applied to chemical energy storage device, such as field of batteries.
Among an embodiment, a kind of goods contain described porous silica material or described goods are made up of described porous silica material.
In another preference, described goods comprise lithium ion battery or cell negative electrode material.
Among an embodiment, a kind of battery cathode active material comprises described porous silica material or is made up of described porous silica material.
Among an embodiment, a kind of negative material comprises described porous silica material as negative active core-shell material.
In another preference, described negative material also comprises conductive agent and/or adhesive.
In another preference, among described negative material, the content of described porous silica material is 60-80wt%.
In another preference, the content of described conductive agent is 10-20wt%.
In another preference, the content of described adhesive is 10-20wt%, with the total weight of negative material.
In another preference, in described negative material, described porous silica material, conductive agent, the mass ratio of adhesive three is (70 ± 10): (10 ± 2): (20 ± 2).
Among an embodiment, a kind of battery positive electrode, negative material, electrolyte and barrier film, and described negative material comprises described porous silica material as negative active core-shell material.
Among an embodiment, described negative material is primarily of described porous silica material, and conductive agent and adhesive form.
Comparatively preferred, among described negative material, the content of porous silica material is 60-90wt%, and the content of conductive agent is 10-20%, and the content of adhesive is 10-20wt%.
Wherein, described adhesive comprises the polymeric derivative with carboxyl, but is not limited thereto.
In another preference, described battery also has shell.
The material of described shell is not particularly limited, and can be metal material, non-metal inorganic material, organic material or other composite materials etc.
In another preference, described battery is preferably non-aqueous battery.
Further, described barrier film can be this area any one battery diaphragm existing, as Teflon septum, ceramic porous membrane, fibreglass diaphragm etc., and is not limited thereto.
Among an embodiment, described electrolyte comprises one or more electrolytic salts and/or one or more solvents.
In another preference, described electrolytic salt comprises cation, such as, can use lithium salts.Preferred lithium salts comprises lithium hexafluoro phosphate, lithium perchlorate, lithium chloride, lithium bromide etc., but is not limited thereto.
In another preference, described battery is lithium battery, and described electrolytic salt is selected from lithium salts, but is not limited thereto.
In another preference, described electrolytic salt meets following requirement: in charging process, the cation of described electrolytic salt can pass electrolyte, negative material is arrived from positive electrode, and in discharge process, the cation of described electrolytic salt can pass electrolyte, arrives positive electrode from negative material.
In another preference, described preferred solvents ground is organic solvent, such as include, but are not limited to methyl ethyl carbonate (MethylEthylCarbonate), dimethyl carbonate (DimethylCarbonate), diethyl carbonate (DiethylCarbonate), ethylene carbonate (EthyleneCarbonate), propene carbonate (PropyleneCarbonate), 1,2-dimethoxy-ethane, 1,3 dioxolanes, methyl phenyl ethers anisole, acetic acid esters, propionic ester, butyrate, diethyl ether, acetonitrile, propionitrile.
In another preference, described organic solvent comprises the cyclic carbonate derivative that at least one is replaced by one or more halogen atom, fluoro-1, the 3-dioxane penta-2-ketone of such as 4-, but is not limited thereto, and it can improve the cycle performance of electrode.
Described electrolyte solvent can be used alone, and also can comprise two kinds or multi-solvents, electrolytic salt can be used alone, and also can comprise two kinds or multiple lithium salts.
Postscript, inventor finds through great many of experiments, when using porous silica material of the present invention directly as negative active core-shell material and aforesaid various electrolyte, when particularly various lithium-ion battery electrolytes coordinates, all show coulombic efficiency (close to 90%) first, the features such as high charge-discharge specific capacity and circulating battery stabilised efficiency, show that porous silica material of the present invention has quite good universality.
Described positive electrode has no particular limits, and can select with reference to state of the art, or adopts the existing positive electrode in this area.
In a preference, described positive electrode comprises one or more reactive metal oxides as positive electrode active materials, and in described reactive metal oxides, also comprise the inactive metal element being selected from lower group: manganese (Mn), iron (Fe), cobalt (Co), vanadium (V), nickel (Ni), chromium (Cr), or its combination, and be not limited thereto.
Preferably, described positive electrode also comprises the component being selected from lower group: the metal oxide of inactive metal, metal sulfide, transition metal oxide, transient metal sulfide, or its combination, and is not limited thereto.
In another preference, aforesaid active metal is lithium.
In another preference, when described battery is lithium battery, described positive electrode also comprises the component being selected from lower group:
LiMnO
2，
LiMn
2O
4，
LiCoO
2，
Li
2CrO
7，
LiNiO
2，
LiFeO
2，
LiNi
xCo
1-XO
2(0<x<1)，
LiFePO
4，
LiMn
zni
1-Zo
2(0<z<1, such as LiMn0.5Ni0.5O2),
LiMn
0.33Co
0.33Ni
0.33O
2，
LiMc
0.5mn
1.5o
4, Mc is divalent metal;
LiNi
xco
yme
zo
2, Me represents one in Al, Mg, Ti, B, Ga, Si or several element, x>0; Y<1, z<1,
Transition metal oxide,
Transient metal sulfide,
Or its combination.
Wherein, described transition metal oxide can preferably from but be not limited to MnO
2, V
2o
5deng.
Wherein, described transient metal sulfide can preferably from but be not limited to FeS
2, MoS
2, TiS
2deng.
Wherein, lithium ion transition metal oxide obtains more application, and comparatively preferably, it can be selected from LiMn
2o
4, LiCoO
2, LiNi
0.8co
0.15al
0.05o
2, LiFePO
4and LiNi
0.33mn
0.33co
0.33o
2in one or more, and to be not limited thereto.
The present invention is set forth further below in conjunction with specific embodiment.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Postscript, unless otherwise indicated, otherwise following percentage and number are all calculated by weight.
The preparation of embodiment 1 porous silicon negative active core-shell material (i.e. " porous silica material "):
1) take 2g metallurgy iron silicon alloy, 2g absolute ethyl alcohol and 16g agate abrading-ball, join 100ml agate jar respectively.
2) ball grinder is put into ball mill, setting ball milling parameter, rotating speed 300r/min, operating time 24h, often work 20min rest 10min.
3) by form of small iron particles silicon alloy suction filtration good for ball milling, washing, oven dry.
4) hydrochloric acid solution measuring 100ml2M puts into the beaker of 200ml, slowly adds form of small iron particles silicon alloy, and constantly stirs until add complete.Beaker is put into ultrasonic instrument ultrasonic disperse 30min.Remove beaker to be placed on magnetic stirring apparatus and to stir 24h continuously.Suction filtration, oven dry.
5) sample through HCl treatment is joined in the hydrofluoric acid solution of 10%, Keep agitation 24h.Suction filtration, washing, oven dry, obtained porous silica material.
Crystalline phase is carried out to porous silicon negative active core-shell material prepared by the present embodiment, pore-size distribution and morphology analysis.Be illustrated in figure 1 its XRD collection of illustrative plates, as can be seen from this collection of illustrative plates, prepared porous silicon is pure phase silicon materials.Fig. 2 is the graph of pore diameter distribution of porous silica material, even aperture distribution, and the duct of illustrative material presents a kind of hierarchy.The SEM photo of Fig. 3, Fig. 4 difference porous silica material and TEM photo, as can be seen from Fig. 3, Fig. 4, the porous silica material preparing gained presents unique pore passage structure, and particle diameter yardstick is 1 ~ 2 μm.
The chemical property analysis of porous silicon negative active core-shell material lithium battery:
By porous silica material, conductive agent and adhesive be 70:10:20 Homogeneous phase mixing proportionally, and is applied on carrying object.Wherein conductive agent is carbon black (SuperP), and adhesive is sodium carboxymethylcellulose (CMC).
The assembling of battery is carried out in the glove box being full of argon gas.Be wherein lithium electrode to electrode, electrolyte is 1M lithium hexafluoro phosphate (LiPF
6) 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.Aforesaid LiPF
6, FEC, DMC, EMC can also substitute with other listed above solute and solvent.
Test condition: survey pole piece load capacity be 1.5mg/cm
2, test under the current condition such as 50mA/g, 100mA/g, 200mA/g, 500mA/g, 1000mA/g, 2000mA/g, 5000mA/g, 10000mA/g respectively.As shown in table 1 below, test under 500mA/g discharge and recharge condition (activating under the current density of front two circles at 50mA/g), after multiple circulation, porous silica material still keeps good cyclical stability, and charge specific capacity conservation rate is 81.5% (under 500mA/g condition).Fig. 5, Fig. 6 are cycle performance figure and the high rate performance figure of porous silicon negative material respectively.In the high rate performance figure of Fig. 6, under the current density of 5000mA/g, the reversible capacity of this material, still up to 550mAh/g, shows hierarchy duct and has good electronics and ion transmission performance.
Table 1 embodiment 1 porous silica material is as the cycle performance test result of negative active core-shell material
The preparation of embodiment 2 porous silicon negative active core-shell material:
1) take in argon atmosphere and take 2g metallurgy iron silicon alloy respectively, 1g absolute ethyl alcohol and 8g agate abrading-ball, join 100ml agate jar respectively.
2) ball grinder is put into ball mill, setting ball milling parameter, rotating speed 400r/min, operating time 12h, often work 10min rest 10min.
3) by form of small iron particles silicon alloy suction filtration good for ball milling, washing, oven dry.
4) hydrofluoric acid solution measuring 100ml10% puts into the plastic beaker of 200ml, slowly adds form of small iron particles silicon alloy, and constantly stirs until add complete.Beaker is put into ultrasonic instrument ultrasonic disperse 30min.Remove beaker to be placed on magnetic stirring apparatus and to stir 12h continuously.Suction filtration, washing, oven dry, obtained porous silica material.
Test porous silica material that the present embodiment obtains according to embodiment 1 similar manner, its cycle performance test result as shown in Figure 7.
The preparation of embodiment 3 porous silicon negative active core-shell material:
1) take in argon atmosphere and take 2g metallurgy iron silicon alloy respectively, 0.4g absolute ethyl alcohol and 2g zirconia ball, join 100ml zirconia ball grinding jar respectively.
2) ball grinder is put into ball mill, setting ball milling parameter, rotating speed 200r/min, operating time 64h, often work 20min rest 10min.
3) by form of small iron particles silicon alloy suction filtration good for ball milling, washing, oven dry.
4) hydrofluoric acid solution measuring 100ml10% puts into the plastic beaker of 200ml, slowly adds form of small iron particles silicon alloy, and constantly stirs until add complete.Beaker is put into ultrasonic instrument ultrasonic disperse 30min.Remove beaker to be placed on magnetic stirring apparatus and to stir 1h continuously.Suction filtration, washing, oven dry, obtained porous silica material.
Test porous silica material that the present embodiment obtains according to embodiment 1 similar manner, its cycle performance test result as shown in Figure 8.
The preparation of embodiment 4 porous silicon negative active core-shell material:
1) take in argon atmosphere and take 2g metallurgy iron silicon alloy respectively, 10g absolute ethyl alcohol and 40g steel ball, join 200ml steel ball grinder respectively.
2) ball grinder is put into ball mill, setting ball milling parameter, rotating speed 500r/min, operating time 1h, often work 10min rest 10min.
3) by form of small iron particles silicon alloy suction filtration good for ball milling, washing, oven dry.
4) hydrofluoric acid solution measuring 100ml10% puts into the plastic beaker of 200ml, slowly adds form of small iron particles silicon alloy, and constantly stirs until add complete.Beaker is put into ultrasonic instrument ultrasonic disperse 30min.Remove beaker to be placed on magnetic stirring apparatus and to stir 48h continuously.Suction filtration, washing, oven dry, obtained porous silica material.
Test porous silica material that the present embodiment obtains according to embodiment 1 similar manner, wherein electrolyte changes the ethylene carbonate (EthyleneCarbonate) of 1M lithium hexafluoro phosphate (LiPF6), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) (volume ratio 1:1:1) solution into.Its cycle performance test result as shown in Figure 9.
The preparation of embodiment 5 porous silicon negative active core-shell material:
1) under air conditions, take 2g metallurgy iron silicon alloy and 8g agate abrading-ball, join 100ml agate jar respectively.
2) ball grinder is put into ball mill, setting ball milling parameter, rotating speed 300r/min, operating time 24h, often work 20min rest 10min.
3) form of small iron particles silicon alloy good for ball milling washed, dry.
4) hydrofluoric acid solution measuring 100ml5% puts into the plastic beaker of 200ml, slowly adds form of small iron particles silicon alloy, and constantly stirs until add complete.Beaker is put into ultrasonic instrument ultrasonic disperse 30min.Remove beaker to be placed on magnetic stirring apparatus and to stir 5h continuously.Suction filtration, washing, oven dry, obtained porous silica material.
Test porous silica material that the present embodiment obtains according to embodiment 1 similar manner, its cycle performance test result as shown in Figure 10.
In addition, inventor is also with reference to embodiment 1-3, and replace with other listed process conditions above, such as other multiple rotational speed of ball-mill, Ball-milling Time, ratio of grinding media to material, solvent material ratio, the acid etch reagent of other kind, the acid treatment time etc. of other kind have carried out the production of porous silica material, and test with reference to the pattern, performance etc. of mode to obtained product of embodiment 1, find that its (first) coulombic efficiency, capacity and cyclical stability etc. are all similar to embodiment 1 product.
The preparation of reference examples porous silicon negative active core-shell material:
1) take 2g metallurgy iron silicon alloy, fragmentation is carried out in the method fragmentation adopting physics to cut, and sieves, and obtains the form of small iron particles silicon alloy that domain size distribution is relatively uniform, washing, oven dry.
2) hydrochloric acid solution measuring 100ml2M puts into the beaker of 200ml, slowly adds form of small iron particles silicon alloy, and constantly stirs until add complete.Beaker is put into ultrasonic instrument ultrasonic disperse 30min.Remove beaker to be placed on magnetic stirring apparatus and to stir 24h continuously.Suction filtration, oven dry.
3) sample through HCl treatment is joined in the hydrofluoric acid solution of 10%, Keep agitation 24h.Suction filtration, washing, oven dry, obtained porous silica material.
According to embodiment 1 similar manner, porous silica material that this reference examples obtains is tested, its cycle performance test result is as shown in Figure 11 and table 2, can find out, the negative material chemical property that the charge-discharge performance of the porous silica material prepared without ball-milling treatment is obviously prepared after ball-milling technology regulation and control than the present invention is poor, prove that the present invention makes the performance of material there occurs change by carrying out mechanical ball-milling treatment to ferro-silicium particle early stage, pass through acid etch more afterwards, define the porous silica material with special appearance and structure, show excellent, exceed the chemical property that those skilled in the art expect.
Table 2 reference examples porous silica material is as the cycle performance test result of negative active core-shell material
The foregoing is only the preferred embodiment of the application, be not limited to the application, for a person skilled in the art, the application can have various modifications and variations.Within all spirit in the application and principle, any amendment done, equivalent replacement, improvement etc., within the protection range that all should be included in the application.
Claims (10)
1. a porous silica material, is characterized in that it has diamond lattic structure, belongs to Fd-3m (227) space group, and has the reacting phase that can react with lithium;
Preferably, described porous silica material is of a size of micron or sub-micron rank, and further preferably, the particle diameter of described porous silica material is 0.1 μm ~ 10 μm, is especially preferably 0.5 μm ~ 5 μm;
Preferably, the particle surface of described porous silica material and inside are also distributed with a plurality of duct;
Preferred further, particle surface and the inner duct being distributed with hierarchy of described porous silica material;
Further preferred, micropore accounting 10%-40% in described hierarchy duct, mesoporous accounting 20%-30%, macropore accounting 30%-70%;
Especially preferred, the specific area of described porous silica material is 0.5-50m
2/ g, more preferably 5-25m
2/ g.
2. a preparation method for porous silica material, is characterized in that comprising: carry out mechanical ball-milling treatment to metallurgy iron silicon alloy, carries out acid etch process afterwards, thus obtains described porous silica material.
3. the preparation method of porous silica material according to claim 2, is characterized in that:
In described metallurgy iron silicon alloy, silicone content is 1wt% ~ 99wt%, and the content of metal impurities is 1wt%-99wt%;
Preferably, in described metallurgy iron silicon alloy, silicone content is 20wt% ~ 99wt%, and metals content impurity is 1wt% ~ 80wt%;
Preferably, in described metallurgy iron silicon alloy, silicone content is 50wt% ~ 90wt%, and the content of metal impurities is 10wt% ~ 50wt%;
Preferably, in described metallurgy iron silicon alloy, silicone content is 70wt% ~ 80wt%, and the content of metal impurities is 20wt% ~ 30wt%.
4. the preparation method of porous silica material according to claim 2, is characterized in that:
Described mechanical ball milling comprises wet ball grinding and/or dry ball milling;
And/or the milling atmosphere of described mechanical ball milling comprises air, argon gas, nitrogen, ammonia or argon hydrogen mixed atmosphere;
And/or the rotational speed of ball-mill of described mechanical ball milling is 200r/min ~ 500r/min, preferred from lower group further: 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min;
And/or the Ball-milling Time of described mechanical ball milling is 1h ~ 64h, preferred from lower group further: 1h, 2h, 4h, 8h, 12h, 24h, 36h, 48h, 64h;
And/or the ratio of grinding media to material adopted in described mechanical ball milling is 1:1 ~ 20:1, preferred from lower group further: 1:1,2:1,3:1,4:1,5:1,6:1,8:1,12:1,16:1,20:1;
And/or the abrading-ball adopted in described mechanical ball milling comprises steel ball, agate ball, corundum ball, any one or two or more combinations in tungsten-carbide ball and zirconia ball.
5. the preparation method of the porous silica material according to claim 2 or 4, is characterized in that:
Described mechanical ball milling adopts wet ball grinding, and solvent wherein comprises any one or two or more combinations in deionized water, absolute ethyl alcohol, ethylene glycol and acetone;
And/or described mechanical ball milling adopts wet ball grinding, and solvent material ratio is wherein 1:5 ~ 5:1, preferred from lower group further: 1:5,1:4,1:3,1:2,1:1,2:1,3:1,4:1,5:1.
6. the preparation method of porous silica material according to claim 2, is characterized in that comprising: in acid etch reagent, carry out metal auxiliary acid etching to the ferro-silicium after mechanical ball-milling treatment, obtained porous silica material;
Preferably, described acid etch reagent comprises watery hydrochloric acid, dust technology, dilute sulfuric acid, any one or two or more combinations in hydrofluoric acid;
And/or the method for described acid etch process comprises standing, stir, any one or two or more combinations in ultrasonic process;
And/or the time of described acid etch process is 1h ~ 48h, preferred from lower group further: 1h, 2h, 5h, 8h, 12h, 18h, 36h, 48h.
7. the porous silica material that according to any one of claim 2-6 prepared by method.
8. a cell negative electrode material, is characterized in that:
It comprises as negative active core-shell material, porous silica material as described in claim 1 or 7;
Preferably, described negative material comprises the porous silica material described in 60wt% ~ 80wt%;
Preferably, described negative material also comprises conductive agent and/or adhesive;
Preferred further, described negative material comprises 10wt% ~ 20wt% conductive agent;
Preferred further, described negative material comprises 10wt% ~ 20wt% adhesive;
More preferred, described negative material comprises mass ratio for (70 ± 10): (10 ± 2): the described porous silica material of (20 ± 2), conductive agent and adhesive.
9. a battery, comprises positive electrode, negative material, electrolyte and barrier film, it is characterized in that described negative material comprises porous silica material described in claim 1 or 7 or cell negative electrode material according to claim 8.
10. a device, is characterized in that comprising the porous silica material described in claim 1 or 7, cell negative electrode material according to claim 8 or battery according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510468107.3A CN105047892B (en) | 2015-08-03 | 2015-08-03 | Porous silica material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510468107.3A CN105047892B (en) | 2015-08-03 | 2015-08-03 | Porous silica material, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105047892A true CN105047892A (en) | 2015-11-11 |
| CN105047892B CN105047892B (en) | 2018-07-27 |
Family
ID=54454270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510468107.3A Active CN105047892B (en) | 2015-08-03 | 2015-08-03 | Porous silica material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105047892B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609740A (en) * | 2016-03-01 | 2016-05-25 | 中国科学院化学研究所 | Silicon alloy composite microspheres and preparation method and application thereof |
| CN106684364A (en) * | 2017-01-26 | 2017-05-17 | 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 |
| 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 |
| CN107611416A (en) * | 2017-08-15 | 2018-01-19 | 武汉科技大学 | A kind of Si-C composite material, its preparation method and application |
| CN108011090A (en) * | 2017-12-03 | 2018-05-08 | 深圳万佳互动科技有限公司 | Prepare method, the battery cathode prepared by this method and the lithium ion battery of negative electrode of 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 |
| WO2018205761A1 (en) * | 2017-05-09 | 2018-11-15 | 武汉科技大学 | Method for preparing three-dimensional porous silicon by taking silicate glass as raw material |
| WO2018205665A1 (en) * | 2017-05-09 | 2018-11-15 | 武汉科技大学 | Method for preparing ant-nest like porous silicon used for lithium ion battery |
| CN109478642A (en) * | 2016-08-18 | 2019-03-15 | 株式会社Lg化学 | Negative electrode material comprising silicon wafer and the method for preparing silicon wafer |
| 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 |
| CN113169324A (en) * | 2021-02-26 | 2021-07-23 | 上海杉杉科技有限公司 | Porous negative electrode active material and method for producing same |
| WO2021195914A1 (en) * | 2020-03-31 | 2021-10-07 | 宁德新能源科技有限公司 | Negative electrode material, negative pole piece, electrochemical apparatus and electronic apparatus |
| CN114988413A (en) * | 2022-05-05 | 2022-09-02 | 昆明理工大学 | Method for preparing high-purity porous silicon |
| CN115642292A (en) * | 2022-12-26 | 2023-01-24 | 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100452493C (en) * | 2003-01-06 | 2009-01-14 | 三星Sdi株式会社 | 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
Non-Patent Citations (1)
| Title |
|---|
| MINGYUAN GE等: "Large-Scale Fabrication，3D Tomography，and Lithium-Ion Battery Application of Porous Silicon", 《NANO LETT.》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609740A (en) * | 2016-03-01 | 2016-05-25 | 中国科学院化学研究所 | Silicon alloy composite microspheres and preparation method and application thereof |
| 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 |
| CN109478642A (en) * | 2016-08-18 | 2019-03-15 | 株式会社Lg化学 | Negative electrode material comprising silicon wafer and the method for preparing silicon wafer |
| CN109478642B (en) * | 2016-08-18 | 2022-05-03 | 株式会社Lg化学 | Negative electrode material containing silicon wafer and method for preparing silicon wafer |
| US11302913B2 (en) | 2016-08-18 | 2022-04-12 | Lg Chem, Ltd. | Negative electrode material comprising silicon flakes and preparing method of silicon flakes |
| CN106684364B (en) * | 2017-01-26 | 2020-04-24 | 南京大学 | Nano porous material and preparation method thereof |
| CN106684364A (en) * | 2017-01-26 | 2017-05-17 | 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 |
| WO2018205761A1 (en) * | 2017-05-09 | 2018-11-15 | 武汉科技大学 | Method for preparing three-dimensional porous silicon by taking silicate glass as raw material |
| WO2018205665A1 (en) * | 2017-05-09 | 2018-11-15 | 武汉科技大学 | Method for preparing ant-nest like porous silicon used for lithium ion battery |
| US11245112B2 (en) | 2017-05-09 | 2022-02-08 | Wuhan University Of Science And Technology | Preparation method of ant nest like porous silicon for lithium-ion battery |
| 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 |
| CN107611416A (en) * | 2017-08-15 | 2018-01-19 | 武汉科技大学 | A kind of Si-C composite material, its preparation method and application |
| 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 |
| CN108011090A (en) * | 2017-12-03 | 2018-05-08 | 深圳万佳互动科技有限公司 | Prepare method, the battery cathode prepared by this method and the lithium ion battery of negative electrode of 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 |
| 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 |
| WO2021195914A1 (en) * | 2020-03-31 | 2021-10-07 | 宁德新能源科技有限公司 | Negative electrode material, negative pole piece, electrochemical apparatus and electronic apparatus |
| CN113728466A (en) * | 2020-03-31 | 2021-11-30 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical device, and electronic device |
| CN113169324A (en) * | 2021-02-26 | 2021-07-23 | 上海杉杉科技有限公司 | Porous negative electrode active material and method for producing same |
| CN114988413A (en) * | 2022-05-05 | 2022-09-02 | 昆明理工大学 | Method for preparing high-purity porous silicon |
| CN114988413B (en) * | 2022-05-05 | 2024-03-15 | 昆明理工大学 | Method for preparing high-purity porous silicon |
| CN115642292A (en) * | 2022-12-26 | 2023-01-24 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105047892B (en) | 2018-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105047892B (en) | Porous silica material, preparation method and application | |
| CN107369825B (en) | Nitrogen-doped carbon-coated manganese oxide lithium ion battery composite negative electrode material and preparation method and application thereof | |
| CN105226285B (en) | A kind of porous Si-C composite material and preparation method thereof | |
| CN107275590A (en) | A kind of porous Si-C composite material and its preparation method and application | |
| CN109167035A (en) | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation | |
| CN109148859B (en) | Preparation method of manganese oxide composite material coated by double carbon layers | |
| CN110299516A (en) | The preparation method of carbon nano pipe array load lithium titanate flexible electrode material | |
| CN108658119B (en) | Method for preparing copper sulfide nanosheet and compound thereof by low-temperature vulcanization technology and application | |
| CN104518207B (en) | A kind of lithium ion battery anode active material and preparation method, anode and lithium ion battery | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN101609884A (en) | A kind of lithium ion battery negative material SnS 2The preparation method | |
| CN104183832A (en) | Preparation method and application of FeF3 flexible electrode based on carbon nano tube-graphene composite three-dimensional network | |
| CN107902633A (en) | A kind of selenizing pyrite material and its battery of preparation | |
| CN102751489B (en) | Method for preparing anode material of lithium ion battery | |
| JP2022539930A (en) | Negative electrode active material, and electrochemical device and electronic device using the same | |
| CN106960947A (en) | Composite, its preparation method and application | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN109279663B (en) | Borate sodium-ion battery negative electrode material and preparation and application thereof | |
| CN103378355B (en) | Alkali metal secondary battery and the preparation method of negative electrode active material, negative material, negative pole and negative electrode active material | |
| CN106654266A (en) | Preparation method of nano-particle/carbon composite material and electrode battery | |
| CN105895878A (en) | Lithium titanate modified material and preparation method thereof | |
| CN105024055A (en) | Lithium-ion battery porous nanometer silicon-carbon composite negative electrode material and preparation method thereof | |
| CN108878823B (en) | Preparation method of metal olivine coated nano silicon | |
| CN103236543B (en) | Method for preparing lithium ferrous silicate anode material | |
| CN111129493B (en) | Transition metal sulfide positive electrode material of sodium ion battery and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |