CN110357111A - Oxidation Asia silicium cathode material based on silicon ash, preparation method and lithium ion battery - Google Patents

Oxidation Asia silicium cathode material based on silicon ash, preparation method and lithium ion battery Download PDF

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CN110357111A
CN110357111A CN201910626427.5A CN201910626427A CN110357111A CN 110357111 A CN110357111 A CN 110357111A CN 201910626427 A CN201910626427 A CN 201910626427A CN 110357111 A CN110357111 A CN 110357111A
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cathode material
oxidation
silicium cathode
silicon ash
sub
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郑洪河
王艳
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Suzhou University
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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 preparation method of the sub- silicium cathode material of the oxidation that the invention discloses a kind of based on silicon ash, comprising the following steps: S1: selection SiO2The spherical silicon ash powder raw material that content is 90% or more, partial size is 100~500 nanometers, pickling remove impurity therein；S2: being restored the wollastonite powder feedstock portions using reduction method, is generated and is aoxidized sub- silicon materials；S3: removing remaining reducing agent, obtains the oxidation Asia silicium cathode material based on silicon ash.The present invention also provides the oxidation Asia silicium cathode material prepared by the method, cathode of lithium battery and lithium ion battery.The preparation method of the sub- silicium cathode material of oxidation of the invention, can be greatly lowered the cost and cost of silicium cathode material, can effectively improve the recycling market of wollastonite powder, while provide a kind of new important selection again to develop lithium ion battery negative material.

Description

Oxidation Asia silicium cathode material based on silicon ash, preparation method and lithium ion battery
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of oxidation Asia silicium cathode material based on silicon ash, Preparation method and the lithium ion battery manufactured with the composite negative pole material.
Background technique
Wollastonite powder is also silicon ash or cohesion silicon ash, is ferroalloy in smelting duriron and industrial silicon (metallic silicon), mine heat The very strong SiO of a large amount of volatility is produced in electric furnace2With Si gas, gas discharge after with air rapid oxidation condense precipitating and At.It is the by-product during big industry is smelted, and whole process needs to be recycled with dedusting environment friendly equipment, because density is smaller, It also needs to be encrypted with encryption equipment.
Wollastonite powder nature is white, and main component is silica, content generally 90% or more or even higher, Average grain diameter 100-500nm, while also containing some impurity such as sodium oxide molybdena, calcium oxide, magnesia, iron oxide, aluminium oxide etc..It is micro- Silicon powder is a kind of important inorganic non-metallic material, and a kind of utilizable important silicon source, due to it is tiny with particle, The excellent physicochemical properties such as large specific surface area, activity be strong are gradually transformed by trade waste as a kind of important material, extensively It is general to be applied to the fields such as cement, concrete, ceramics, chemical industry, refractory material, composite material, but in field of lithium ion battery extremely The present is not effectively utilized.
In lithium ion battery industry, sub- silicon (SiO is aoxidizedx) be used as negative electrode material have specific capacity is high, bulk effect is small, The excellent equal prominent feature of cycle performance, has obtained more and more applications, 20%- is especially added in graphite cathode material 40% SiOxCathode specific capacity can be significantly improved, to improve the specific energy of battery, can also be improved to a certain extent The safety of cathode.SiOxWith stronger electro-chemical activity, in process of intercalation, react with lithium ion generation first LiO2、Li4SiO4With simple substance Si；Next, simple substance Si and Li+Further reaction generates lithium-silicon alloy, in the process, LiO2 And Li4SiO4It can be used as buffer layer and alleviate charge and discharge bring volume expansion problem, effectively maintain the complete of material structure Property.However, SiOxMaterial intrinsic conductivity itself is lower, and lithium ion transport resistance is also bigger, this is also limited to a certain extent It has been made in the application of field of lithium ion battery.
SiO at presentxPreparation method mostly use the method for partical oxidation or high-purity SiO of nano silica fume2Partial reduction Method mostly uses high-purity nm Si powder or high-purity Si O in these preparation methods2For fine raw material, former material preparation method for material is answered Miscellaneous cumbersome, low yield is expensive, it is difficult to is mass produced.Therefore, find it is a kind of have cheap, 100 nano particle sizes and Spherical silicon powder body raw material is most important to the development of the industry.The scrap silicon of solar panel is a kind of cheap elemental silicon material Material, although having the characteristics that cheap, its dopant species complexity, the spherical morphology without feature, and lot stability is poor, though A possibility that right to have passed through prolonged research and explore, but this silicon materials are directly used in negative electrode of lithium ion battery, is little.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind with low price, abundance, can satisfy The pattern of silicium cathode and the silicon ash of particle size range prepare the technology for aoxidizing sub- silicium cathode material as raw material.
The preparation method of the sub- silicium cathode material of the oxidation that it is an object of that present invention to provide a kind of based on silicon ash, including following step It is rapid:
S1: selection SiO2The spherical silicon ash powder raw material that content is 90% or more, partial size is 100~500 nanometers, pickling remove Impurity therein；
S2: being restored the wollastonite powder feedstock portions using reduction method, is generated and is aoxidized sub- silicon materials；
S3: removing remaining reducing agent, obtains the oxidation Asia silicium cathode material based on silicon ash.
In the present invention, the silicon ash powder raw material is a kind of high purity silicon ash powder material with nano-scale, spherical morphology Material, it is ferroalloy during smelting duriron and industrial silicon (metallic silicon), and it is very strong that a large amount of volatility are generated in ore-smelting electric furnace SiO2With Si gas, after gas discharge and made of air rapid oxidation condensation precipitating, particle size is 100~500nm, SiO2Content is more than 90%.Preferably, the silicon ash powder raw material is purity 98%, the spheric granules of 100~300nm of partial size.
Further, in step S1, the pickling uses hydrochloric acid, nitric acid or both with the mixed acid of arbitrary proportion, removal Impurity be mainly oxide impurity.Preferably, the pickling uses the hydrochloric acid solution of 0.2M, wash time 1h, later Make to be washed with deionized to neutrality.
Further, in step S2, the reduction method is carbon reduction, pure silicon reduction, magnesiothermic reduction or aluminothermic reduction.It is preferred that Ground, the reducing agent used include Mg, Al, Si or graphite material, and dosage is 10~50wt.% of wollastonite powder.
Further, in step S2, reduction reaction carries out under Ar gas shielded, and reduction temperature is controlled at 800~1800 DEG C.
In the present invention, in step S3, when reducing agent is Mg or Al, remaining reducing agent is removed using white picking；When When using graphite or Si as reducing agent, product is without post-processing.
Further, the white picking uses hydrochloric acid, nitric acid or both with the mixed acid of arbitrary proportion.
Further, further include being dried in vacuo to product, aoxidize sub- silicium cathode material to obtain high-purity nano grade The step of.
Another aspect of the present invention provides the oxidation Asia silicium cathode material being prepared by the method.
The present invention also provides the negative electrode of lithium ion battery and lithium that are prepared by the sub- silicium cathode material of oxidation Ion battery.
The beneficial effects of the present invention are:
1. the present invention is using the by-product wollastonite powder in industry smelting as raw material, cheap, only high performance silicon powder The 1% of price has the market advantage outstanding；Secondly, wollastonite powder has the characteristics that high-purity, nano particle and spherical morphology, Obtained target product equally has the characteristics that these are protruded；Furthermore easy post-processing, whole process only need pickling and reduction Process has apparent advantage compared to the complicated purifying technique of solar power silicon waste material；Finally, the excellent electrical properties of product, by Have the characteristics that suitable granularity, purity and pattern in product, shows that high embedding de- lithium holds as lithium ion battery negative material Amount and excellent cycle performance.
2. oxidation Asia silicium cathode material preparation method of the invention can be greatly lowered the cost of silicium cathode material and make Valence can effectively improve the recycling market of wollastonite powder, while provide one kind again to develop lithium ion battery negative material New important selection.Be of great significance to the following cost for reducing lithium ion battery and cost, be develop the following high-performance, The important selection of inexpensive silicon based anode material.
Detailed description of the invention
Fig. 1 is the SEM figure for the silicon materials for using and obtaining in each step in embodiment 1: (a) the SEM figure of silicon ash raw material, (b) SiO after magnesiothermic reductionxThe SEM of material schemes, the SiO after (c) post-processingxThe SEM of material schemes.
Fig. 2 is the XRD diagram of material in each step in embodiment 1: (a) XRD diagram of silicon ash raw material, (b) after a pickling XRD diagram, (c) SiO after magnesiothermic reductionxXRD diagram.
Fig. 3 is to obtain SiO in embodiment 1xThe cyclic voltammetry curve figure of product.
Fig. 4 is SiO obtained in embodiment 1xProduct is used as the long-term cycle performance of lithium ion battery negative material.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with It more fully understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
By taking reducing agent selects magnesium powder as an example, the specific method is as follows for the present embodiment:
(a) choosing average grain diameter is 120 nanometers of wollastonite powder as raw material, and purity 98%, impurity includes iron oxide, oxidation Magnesium, calcium oxide and a small amount of carbon.
(b) it after silicon ash powder raw material to be put into HCl solution high speed agitator treating 1 hour of 0.1M, filters and uses deionization It water washing 3 times, until solution is weakly acidic, is dried for standby.
(c) by after pickling silicon ash powder raw material and magnesium powder according to the quality of 1:0.8 than ground and mixed after, the Ar in tube furnace Under atmosphere protection, 650 DEG C of calcining 1h after partial reduction, obtain SiOxMaterial.
(d) SiO that will be obtainedxMaterial is dispersed in the HCl solution of 0.05M, is reacted overnight under magnetic agitation, is further removed The magnesium powder of decontamination and remnants, after washing and being collected by centrifugation, 120 DEG C of vacuum drying obtain the SiO of high-purityxNegative electrode material.
Embodiment 2
Reducing agent selects aluminium powder, and specific method is similar to Example 1, except that by the silicon ash powder raw material after pickling With high purity aluminum powder according to the quality of 1:0.6 than ground and mixed after, in tube furnace under Ar atmosphere protection, 800 DEG C of calcining 1.5h are obtained To the SiO containing partial reductionxMaterial, obtained SiOxMaterial is dispersed to the HNO of 0.1M3In solution, reacted under magnetic agitation Night further removes the magnesium powder of impurity and remnants, and after washing and being collected by centrifugation, 120 DEG C of vacuum drying obtain high-purity and height The SiO of performancexNegative electrode material.
Embodiment 3
Reducing agent selects graphitic carbon, and specific method is similar to Example 1, except that the wollastonite powder after pickling is former Material and the graphite composite powder of 1 micron of size of partial size according to the quality of 1:1 than ground and mixed after, in tube furnace under Ar atmosphere protection, 1200 DEG C of calcining 3h, obtain the SiO containing partial reductionxMaterial after naturally cooling to 500 DEG C, is passed through air thermal preservation 3h, removes more Remaining graphitic carbon material obtains high-purity and high performance SiOxNegative electrode material.
Embodiment 4
Reducing agent selects high-purity silicon powder, and specific method is similar to Example 1, except that by the wollastonite powder after pickling The high-purity Si powder of raw material and 100 nanosized of partial size according to the quality of 1:0.5 than ground and mixed after, the Ar atmosphere in tube furnace Under protection, 1000 DEG C of calcining 3h obtain the SiO containing partial reductionxMaterial obtains high-purity after naturally cold under Ar gas shielded With high performance SiOx negative electrode material.
Attached drawing 1 is the SEM figure for the silicon materials for using and obtaining in each step in embodiment 1.It can be seen from the figure that former material Expect that ball-type is presented in particle, but the distribution of the diameter of ball is different, does not wait (attached drawing 1a) in 100-300nm.After magnesium thermit, material Material is still able to maintain ball-type, and size does not also change significantly, and the surface of ball obviously becomes coarse, and the profile of entire ball is not as good as former Material is mellow and full (attached drawing 1b), this illustrates SiO2It is successfully reacted with Mg powder.Material after pickling, after pickling Equally maintain the scale (attached drawing 1c) of ball-type pattern and nanometer.
The situation of change of XRD diagram is as shown in Fig. 2, and the XRD after raw material pickling only has 21 ° of a very wide peak, this It is SiO2Characteristic peak, since the crystallinity of material itself is not high, peak shape is not sharp.After magnesiothermic reduction, SiOxPeak occur, Illustrate that the material becomes SiO by successfully reductionx, have also appeared some miscellaneous peaks at the same time, these miscellaneous peaks mainly with do not have in material There is the Mg reacted completely related.After overpickling, the peak of Mg is completely disappeared, and shows that Mg is completely removed in this process, most The corresponding peak of final product is high-purity SiOxMaterial.
The SiO that attached drawing 3 isxFirst three circle cyclic voltammetry curve figure of material.In first circle negative sense scanning process, first It is that 1.4V or so a very faint reduction peak occurs, corresponding is SiOxSEI film is formed during material initial charge Process.Continue to scan to low potential, an apparent reduction peak occurs in 0.03V or so, corresponding reaction is lithium ion Li is formed in insertion silicon materialsxThe process of Si alloying, during subsequent forward scan, material 0.32V and 0.5V again Respectively there is an oxidation peak, corresponding is LixThe removal alloying process of Si.
Attached drawing 4 is the material in 320mA g-1High current density under 200 circle cycle performance figures, it can be seen that most Final product SiOxReversible capacity in the cyclic process for the first time of material is in 1000mAh g-1, with current commodity SiOxThe appearance of material Quite, after the chemical conversion of preceding 8 circle, what the charge/discharge capacity of battery can be more stable is maintained at 800mAh g to amount-1Left and right, This capacity is still conventional graphite electrodes material more than twice, and without apparent inducing capacity fading, illustrates this inexpensive material Material is applied to the feasibility of lithium ion battery.
To sum up, this silicon ash powder material with low cost, raw material abundance provided by the invention, prepares after reduction SiOxScheme of the material for negative electrode of lithium ion battery has higher feasibility.Not only raw material itself is cheap and easy to get, final product SiOxMaterial is even more nanosizing, the feature of spherical shape and high-purity for inheriting raw material, has most suitable particle size range and shape Looks, Electrochemical results show that material shows the high capacity and excellent cycle performance for aoxidizing sub- silicon materials, in future There is important application and development prospect in high specific energy commercial lithium-ion batteries.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention Protection scope within.Protection scope of the present invention is subject to claims.

Claims (10)

1. a kind of preparation method of the sub- silicium cathode material of oxidation based on silicon ash, which comprises the following steps:
S1: selection SiO2The spherical silicon ash powder raw material that content is 90% or more, partial size is 100~500 nanometers, pickling remove wherein Impurity；
S2: being restored the wollastonite powder feedstock portions using reduction method, is generated and is aoxidized sub- silicon materials；
S3: removing remaining reducing agent, obtains the oxidation Asia silicium cathode material based on silicon ash.
2. the preparation method of the sub- silicium cathode material of oxidation as described in claim 1 based on silicon ash, which is characterized in that step S1 In, the pickling uses hydrochloric acid, nitric acid or both with the mixed acid of arbitrary proportion.
3. the preparation method of the sub- silicium cathode material of oxidation as described in claim 1 based on silicon ash, which is characterized in that step S2 In, the reduction method is carbon reduction, pure silicon reduction, magnesiothermic reduction or aluminothermic reduction.
4. the preparation method of the sub- silicium cathode material of oxidation as described in claim 1 based on silicon ash, which is characterized in that step S2 In, reduction reaction carries out under Ar gas shielded, and reduction temperature is controlled at 800~1800 DEG C.
5. the preparation method of the sub- silicium cathode material of oxidation as described in claim 1 based on silicon ash, which is characterized in that step S2 In, the reducing agent used includes Mg, Al, Si or graphite, and dosage is 10~50wt.% of wollastonite powder.
6. the preparation method of the sub- silicium cathode material of oxidation as claimed in claim 5 based on silicon ash, which is characterized in that step S3 In, when reducing agent is Mg or Al, remaining reducing agent is removed using white picking.
7. the preparation method of the sub- silicium cathode material of oxidation as claimed in claim 6 based on silicon ash, which is characterized in that described two Secondary pickling uses hydrochloric acid, nitric acid or both with the mixed acid of arbitrary proportion.
8. the oxidation Asia silicium cathode material that described in any item methods are prepared according to claim 1~7.
9. the negative electrode of lithium ion battery according to claim 8 for aoxidizing sub- silicium cathode material and being prepared.
10. a kind of lithium ion battery, which is characterized in that including negative electrode of lithium ion battery as claimed in claim 9.
CN201910626427.5A 2019-07-11 2019-07-11 Oxidation Asia silicium cathode material based on silicon ash, preparation method and lithium ion battery Pending CN110357111A (en)

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CN112397701A (en) * 2020-11-20 2021-02-23 江苏科技大学 Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof
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Publication number Priority date Publication date Assignee Title
CN111115639A (en) * 2019-12-25 2020-05-08 湖北万润新能源科技发展有限公司 Preparation of SiO by centering reactionxMethod and application of @ C material
CN112397701A (en) * 2020-11-20 2021-02-23 江苏科技大学 Rice husk-based silicon oxide/carbon composite negative electrode material and preparation method and application thereof
CN112290005A (en) * 2020-11-23 2021-01-29 山东硅纳新材料科技有限公司 Method for preparing novel silicon-carbon negative electrode material by utilizing dopamine hydrochloride
CN113991082A (en) * 2021-10-27 2022-01-28 昆明理工大学 Method for preparing silicon-carbon cathode material of lithium ion battery from silica fume
CN113991082B (en) * 2021-10-27 2024-04-16 昆明理工大学 Method for preparing silicon-carbon negative electrode material of lithium ion battery by using silica fume
CN115536027A (en) * 2022-09-27 2022-12-30 湖南宸宇富基新能源科技有限公司 Preparation and application of silica
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