CN107195895A - A kind of silica-base material preparation method using alloy as reducing agent - Google Patents

A kind of silica-base material preparation method using alloy as reducing agent Download PDF

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Publication number
CN107195895A
CN107195895A CN201710017223.2A CN201710017223A CN107195895A CN 107195895 A CN107195895 A CN 107195895A CN 201710017223 A CN201710017223 A CN 201710017223A CN 107195895 A CN107195895 A CN 107195895A
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China
Prior art keywords
silica
alloy
aluminium
base material
magnesium
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CN201710017223.2A
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Chinese (zh)
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包健
范美强
田光磊
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China Jiliang University
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China Jiliang University
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Priority to CN201710017223.2A priority Critical patent/CN107195895A/en
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • 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
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/023—Preparation by reduction of silica or free silica-containing material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/463—Aluminium based
    • 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
    • H01M4/46—Alloys based on magnesium or aluminium
    • H01M4/466—Magnesium based
    • 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
    • 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
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The present invention relates to a kind of silica-base material preparation method using alloy as reducing agent.This method is using silica as presoma, mechanical mixture alloy reducing agent and low melting point salt, briquetting, then in vacuum or inert atmosphere, 150~600 DEG C of 2~10h of sintering；Then salt acid elution, washing, drying obtains silica-base material；Silica is MCM 41, MCM 48, MCM 50, SBA 15 one kind；Alloy reducing agent is one kind of magnesium alloy and aluminium alloy；Magnesium alloy is magnalium, magnesium lithium, magnesium calcium, one kind of magnesium sodium；Aluminium alloy is aluminium sodium, aluminium lithium, aluminium calcium, one kind of aluminium potassium；Low melting point salt is aluminium chloride, aluminium bromide, zinc chloride, one kind of zinc bromide；The mol ratio 2~4 of alloy and silica；The mol ratio of low melting point salt and silica is 3~10；Silica-base material particle size prepared by the present invention is small, loose structure, available for lithium ion battery negative material or portable hydrogen material, with extraordinary application prospect.

Description

A kind of silica-base material preparation method using alloy as reducing agent
Technical field
The present invention relates to a kind of preparation method of electrode material, and in particular to a kind of silica-base material using alloy as reducing agent Preparation method.
Background technology
Silicon rich reserves, lithium storage content are high, are the lithium ion battery negative materials for having very much application prospect.But elemental silicon is deposited It is poor in electric conductivity, combined with lithium rear volumetric expansion it is big and make active material from electrode surface come off the problems such as, constrain silicon electricity The promotion and application of pole material.At present, scientific research personnel is using good conductivity, specific surface area big metal, carbon material and polymer Surface coating silicon, improves the chemical property of silicon electrode material to a certain degree.
Magasinski [Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J, YushinG.Nat.Mater., 2010,9 (4)：353-358.] heat treatment carbon black, using CVD by nanometer siliceous deposits carbon black table Face, obtains Si-C composite material.The material shows preferable chemical property.Kummer [Kummer M, Badillo JP, Schmitz A.J Electrochem Soc, 2014,161 (1)：] etc. A40-A45. n-S i/P A N i composites are prepared, The material shows preferable electric conductivity, pliability, effectively Volume Changes of the compacting silicon in charge and discharge cycles.Wang [Wang X, Wen Z, Liu Y, Wu X.Electrochim.Acta, 2009,54 (20)：4662-4667.] etc. using mechanical attrition method be combined Lithium, silica, tin oxide and graphite, obtain Si-Sn-Li4SiO4/ C composite.Capacity after 100 circulations of the material is more than 600mAh/g.At present, there is certain defect in existing silica-base material preparation technology.Silicon substrate is prepared using mechanical attrition method Material, it is impossible to effectively realize that composition is dispersed；And use CVD preparation cost too high, the operation temperature of high temperature thermal reduction silica Degree is higher than 700 DEG C, and energy consumption is too big.
The content of the invention
Present invention aims at a kind of silica-base material preparation method using alloy as reducing agent is provided, existing preparation skill is overcome The defect of art, improves the chemical property of silicon electrode material.For achieving the above object, the technical scheme is that：Silicon Sill is using silica as presoma, mechanical mixture alloy reducing agent and low melting point salt, briquetting, then in vacuum or indifferent gas Atmosphere, 150~600 DEG C of 2~10h of sintering；Then salt acid elution, washing, drying obtains silica-base material；Silica is MCM-41, MCM-48, MCM-50, SBA-15 one kind；Alloy reducing agent is one kind of magnesium alloy and aluminium alloy；Magnesium alloy is magnalium, magnesium Lithium, magnesium calcium, one kind of magnesium sodium；Aluminium alloy is aluminium sodium, aluminium lithium, aluminium calcium, one kind of aluminium potassium；Low melting point salt be aluminium chloride, aluminium bromide, One kind of zinc chloride, zinc bromide；The mol ratio 2~4 of alloy and silica；The mol ratio of low melting point salt and silica is 3 ~10；A kind of silica-base material preparation method using alloy as reducing agent includes：
1) alloyed powder, silica and the low melting point salt of certain mass, 1~40h of argon gas atmosphere mechanical ball mill are weighed；
Wherein, the particle size of alloyed powder is 10 nanometers~100 microns；
2) by step 1) product briquet, pressure limit be 2~40 tons；
3) by step 2) product be put into closed container, 150~600 DEG C of inert atmosphere or vacuum shelve 2~10h；Then Cooling, crushing；
4) by step 3) product pour into excessive hydrochloric acid, handle 2~10h；Be separated by filtration, washing and drying, obtain silicon substrate Material.
The silica-base material preparation method that the present invention is provided, compared with other cathode material preparation methods, has the following advantages that：
1) present invention process is simple and convenient to operate, and is conducive to industrialized production.
2) using alloy reducing agent, low melting point salt and silicon dioxde reaction, the temperature that greatly reduction silica is reduced, Reduce energy consumption；
3) the standby silica-base material of patent system of the present invention, can also make intermediate directly as lithium ion battery negative material Further processing prepares negative material, it can also be used to hydrogen manufacturing material, has very in the field such as lithium ion battery and portable hydrogen source Good application prospect.
Embodiment
In order to further understand the content, features and effects of the present invention, hereby lifting following examples, and describe in detail such as Under：
Embodiment 1
A kind of composition design of silica-base material is：
MCM-41,1g；Magnesium alloy, 1g；AlCl3, 8g；
MCM-41,1g；Magnesium lithium alloy, 1g；AlCl3, 8g；
MCM-41,1g；Kalzium metal, 1g；AlCl3, 8g；
A kind of silica-base material preparation method using alloy as reducing agent includes：
1) alloyed powder, silica and the aluminium chloride of certain mass, argon gas atmosphere mechanical ball mill 10h are weighed；
Wherein, the particle size of alloyed powder is 10 nanometers~100 microns；
2) by step 1) product briquet, pressure limit be 10 tons；
3) by step 2) product be put into closed container, 300 DEG C of inert atmosphere or vacuum shelve 5h；Then cool down, crush；
4) by step 3) product pour into excessive hydrochloric acid, handle 5h；Be separated by filtration, washing and drying, obtain silica-base material.
The silica-base material particle size is tiny, and loose structure is presented；During for negative electrode of lithium ion battery；After 100 circulations, When 0.1C discharge capacities are more than 600mAh/g. for portable hydrogen material, silica flour hydrogen in 70 DEG C of 0.1C sodium hydroxide solutions Gas yield is higher than 85%.
Embodiment 2
A kind of composition design of silica-base material is：
SBA-15,1g；Aluminium lithium alloy, 1g；AlCl3, 8g；
SBA-15,1g；Magnesium alloy, 1.5g；AlCl3, 8g；
SBA-15,1g；Magnesium lithium alloy, 2g；AlCl3, 8g；
A kind of silica-base material preparation method using alloy as reducing agent includes：
1) alloyed powder, silica and the aluminium chloride of certain mass, argon gas atmosphere mechanical ball mill 20h are weighed；
Wherein, the particle size of alloyed powder is 10 nanometers~100 microns；
2) by step 1) product briquet, pressure limit be 8 tons；
3) by step 2) product be put into closed container, 250 DEG C of inert atmosphere or vacuum shelve 5h；Then cool down, crush；
4) by step 3) product pour into excessive hydrochloric acid, handle 5h；Be separated by filtration, washing and drying, obtain silica-base material.
The silica-base material particle size is tiny, and loose structure is presented；During for negative electrode of lithium ion battery；After 100 circulations, When 0.1C discharge capacities are more than 600mAh/g. for portable hydrogen material, silica flour hydrogen in 70 DEG C of 0.1C sodium hydroxide solutions Gas yield is higher than 85%.
Embodiment 3
A kind of composition design of silica-base material is：
MCM-41,1g；Aluminium lithium alloy, 1g；ZnCl2, 7g；
MCM-41,1g；Magnesium alloy, 1g；AlBr3, 8g；
SBA-15,1g；Magnesium lithium alloy, 1g；ZnCl2, 8g；
A kind of silica-base material preparation method using alloy as reducing agent includes：
1) alloyed powder, silica and the aluminium chloride of certain mass, argon gas atmosphere mechanical ball mill 15h are weighed；
Wherein, the particle size of alloyed powder is 10 nanometers~100 microns；
2) by step 1) product briquet, pressure limit be 10 tons；
3) by step 2) product be put into closed container, 600 DEG C of inert atmosphere or vacuum shelve 10h；Then cooling, powder It is broken；
4) by step 3) product pour into excessive hydrochloric acid, handle 5h；Be separated by filtration, washing and drying, obtain silica-base material.
The silica-base material particle size is tiny, and loose structure is presented；During for negative electrode of lithium ion battery；After 100 circulations, When 0.1C discharge capacities are more than 600mAh/g. for portable hydrogen material, silica flour hydrogen in 70 DEG C of 0.1C sodium hydroxide solutions Gas yield is higher than 85%.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of changes, modification can be carried out to these embodiments, replace without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (1)

1. a kind of silica-base material preparation method using alloy as reducing agent, it is characterised in that：Silica-base material is using silica before Drive body, mechanical mixture alloy reducing agent and low melting point salt, briquetting, then vacuum or inert atmosphere, 150~600 DEG C of sintering 2~ 10h；Then salt acid elution, washing, drying obtains silica-base material；Silica is MCM-41, MCM-48, MCM-50, SBA-15 One kind；Alloy reducing agent is one kind of magnesium alloy and aluminium alloy；Magnesium alloy is magnalium, magnesium lithium, magnesium calcium, one kind of magnesium sodium；Aluminium Alloy is aluminium sodium, aluminium lithium, aluminium calcium, one kind of aluminium potassium；Low melting point salt is aluminium chloride, aluminium bromide, zinc chloride, one kind of zinc bromide； The mol ratio 2~4 of alloy and silica；The mol ratio of low melting point salt and silica is 3~10；One kind is using alloy as reduction The silica-base material preparation method of agent includes：
1) alloyed powder, silica and the low melting point salt of certain mass, 1~40h of argon gas atmosphere mechanical ball mill are weighed；
Wherein, the particle size of alloyed powder is 10 nanometers~100 microns；
2) by step 1) product briquet, pressure limit be 2~40 tons；
3) by step 2) product be put into closed container, 150~600 DEG C of inert atmosphere or vacuum shelve 2~10h；Then cool down, Crush；
4) by step 3) product pour into excessive hydrochloric acid, handle 2~10h；Be separated by filtration, washing and drying, obtain silica-base material.
CN201710017223.2A 2017-01-06 2017-01-06 A kind of silica-base material preparation method using alloy as reducing agent Pending CN107195895A (en)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN108666560A (en) * 2018-05-15 2018-10-16 欣旺达电子股份有限公司 Lithium ion battery, nano silicon material and preparation method thereof
CN109980191A (en) * 2017-12-28 2019-07-05 上海杉杉科技有限公司 A kind of high coulomb efficiency silicon-carbon cathode material and its preparation method and application
CN112429701A (en) * 2020-12-02 2021-03-02 中国计量大学 Waste silicon wafer treatment method for hydrogen production by hydrolysis
CN112520693A (en) * 2020-12-02 2021-03-19 中国计量大学 Device and process for heat treatment of waste silicon wafers
WO2022242643A1 (en) * 2021-05-19 2022-11-24 Epro Development Limited A process and apparatus for the production of hydrogen

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109980191A (en) * 2017-12-28 2019-07-05 上海杉杉科技有限公司 A kind of high coulomb efficiency silicon-carbon cathode material and its preparation method and application
CN108666560A (en) * 2018-05-15 2018-10-16 欣旺达电子股份有限公司 Lithium ion battery, nano silicon material and preparation method thereof
CN112429701A (en) * 2020-12-02 2021-03-02 中国计量大学 Waste silicon wafer treatment method for hydrogen production by hydrolysis
CN112520693A (en) * 2020-12-02 2021-03-19 中国计量大学 Device and process for heat treatment of waste silicon wafers
WO2022242643A1 (en) * 2021-05-19 2022-11-24 Epro Development Limited A process and apparatus for the production of hydrogen

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Application publication date: 20170922