CN105470480A - Preparation method of tin alloy/silicon/carbon electrode material - Google Patents
Preparation method of tin alloy/silicon/carbon electrode material Download PDFInfo
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- CN105470480A CN105470480A CN201510848742.4A CN201510848742A CN105470480A CN 105470480 A CN105470480 A CN 105470480A CN 201510848742 A CN201510848742 A CN 201510848742A CN 105470480 A CN105470480 A CN 105470480A
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/387—Tin or alloys based on tin
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a tin alloy/silicon/carbon electrode material. The method comprises the following steps: with a porous polymer as a carrier, depositing silicon oxide; mechanically mixing magnesium; carrying out high-temperature thermal reduction and acid treatment; filtering and drying the mixture; mechanically mixing a tin alloy; tabletting the mixture; and carrying out high-temperature sintering to obtain the tin alloy/silicon/carbon electrode material. The porous polymer is one of polyacetylene, polyacrylonitrile, polyaniline, polypyrrole and phenolic resin; the tin alloy is one of a nickel-tin alloy, a copper-tin alloy, an iron-tin alloy and a silver-tin alloy; the silicon source is one of tetraethoxysilane, silicon tetrachloride and trichlorosilane; an inner layer of the tin alloy/silicon/carbon electrode material is carbon and silicon in a porous structure; and an outer layer is the tin alloy with good conductivity and stable structure. The electrode material has the advantages of high specific capacity and long cycle lifetime, and has a good application prospect in the field of batteries.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material, be specifically related to a kind of preparation method of ashbury metal/silicon/carbon electrode material.
Background technology
Lithium ion battery negative material is one of deciding factor of impact whole battery performance, fail safe, cost etc.Commercial Li-ion batteries negative material graphite, its theoretical capacity is 372mAh/g, is difficult to meet the demand of chemical power source of following Large Copacity, high power, low cost.Silicium cathode materials theory lithium storage content (4200mAh/g), rich reserves is a kind of very promising lithium ion battery negative material of future generation.But silicium cathode material is change in volume large (volumetric expansion about 400%) in charge and discharge process, cause that electrode material can break in cyclic process, efflorescence, structural breakdown etc., and the electric conductivity of silicon is very low, cause that irreversible capacity is higher, cyclical stability is poor.Change in volume and its conductivity of raising of how cushioning silicon materials are the keys improved silicium cathode material electrochemical performance He realize its commercial applications.Due to material with carbon element inherently business-like lithium ion battery negative material, cheap, stable performance simultaneously, silico-carbo composite material is the focus of research and development and the selection of Industry Promotion always.
Magasinski [MagasinskiA, DixonP, HertzbergB, KvitA, AyalaJ, YushinG.Nat.Mater., 2010,9 (4): 353-358.] adopt heat treatment carbon black to obtain conducting matrix grain, then use CVD at carbon blacksurface depositing nano silicon and carbon, obtain particle diameter at the Si-C composite material of 15-30 μm.This composite material exhibits goes out very high capacity, excellent circulation and high rate performance.Conducting polymer has higher conductivity, is the good sources of carbon of electrode material.In addition, polymer can provide good dispersiveness, contributes to the generation preventing caking phenomenon.Conducting polymer has elasticity, effectively solves the volumetric expansion problem of electrode material in charge and discharge process, thus improves cyclical stability and the charge-discharge performance of battery.Kummer [KummerM, BadilloJP, SchmitzA.JElectrochemSoc, 2014,161 (1): A40-A45.] etc. nano-silicon (n-Si) active material is combined with the non-active material (polyaniline) being used as binding agent and buffer matrix and prepare n-Si/PANi.This material demonstrates the capacity higher than conventional anode material (graphite) and cyclical stability; After 300 circulations, the theoretical specific capacity of this composite material remains on more than 60%.Relative to softer conducting polymer, metal has the advantages such as good conductivity and mechanical strength, more can limit the change in volume of silicon in charge and discharge process, improve conductivity simultaneously, the contact of isolation silicon materials and electrolyte, suppresses the formation of SEI film.Wang [WangX, WenZ, LiuY, WuX.Electrochim.Acta, 2009,54 (20): 4662-4667.] etc. adopt high-energy ball milling method, with lithium metal reduction SiO and SnO, and add a certain amount of graphite, prepare Si-Sn-Li
4siO
4/ C composite.This material first reversible capacity is about 900mAh/g, and the capability retention after 100 circulations reaches 79.2%.But metallic tin volume in charge and discharge cycles process also can change, and causes structure collapses, is difficult to effectively contain silicon change in volume in the circulating cycle.
Summary of the invention
The object of the invention is the preparation method providing a kind of ashbury metal/silicon/carbon electrode material, overcomes the defect of existing technology of preparing, improves the cycle life of silicon electrode material.For achieving the above object, technical scheme of the present invention is: take porous polymer as carrier, cvd silicon oxide, mechanical mixture magnesium, high-temperature hot reduction, acid treatment, filtering drying, again mechanical mixture ashbury metal, compressing tablet, high temperature sintering, obtain ashbury metal/silicon/carbon electrode material; Porous polymer is that polyacetylene, polypropylene are fine, the one of polyaniline, polypyrrole, phenolic resins; Ashbury metal is the one of nickeltin, signal bronze, ferro-tin alloy, silver-colored ashbury metal; Silicon source is the one of tetraethoxysilane, silicon tetrachloride, trichlorosilane; The preparation method of ashbury metal/silicon/carbon electrode material comprises the steps:
1) porous polymer and the silicon source that weigh certain mass are mixed in organic solvent, stir 1 ~ 10h;
2) in step 1) slowly instill hydrous ethanol solution in mixture, control hydrous ethanol solution drop rate 0.5 ~ 2ml/min: controlled hydrolysis temperature 25 ~ 70 DEG C; Reaction time is 2 ~ 40h; Centrifugation, filtration washing, oven dry obtain how empty polymer/silica;
3) weigh the step 2 of certain mass) product and and magnesium metal mechanical mixture, then 600 ~ 800 DEG C of inert atmosphere thermal reduction 2 ~ 10h; The mol ratio of magnesium/silicon is (2 ~ 5): 1;
4) by step 3) product immersion excessive hydrochloric acid, reaction 2 ~ 40h, filters, washs, dries, acquisition carbon/silicon composite;
5) step 4 of certain mass is weighed) product and ashbury metal powder, inert atmosphere protection, mechanical mixture 1 ~ 20h, controls rotating speed 50-250 rev/min;
6) by step 5) product compressing tablet, inert atmosphere, high temperature 700 ~ 1200 DEG C leave standstill 1 ~ 10h; Obtain ashbury metal/silicon/carbon electrode material.
Organic solvent in described step 1 is the one of methyl alcohol, ethanol, acetone, ethylene glycol, glycerol, oxolane;
Water in described step 2 and the volume ratio of ethanol are 0.05 ~ 0.95; The mol ratio (2 ~ 5) in water and silicon source: 1;
Ashbury metal powder particles size in described step 5 is less than 50 microns;
In described ashbury metal, the mol ratio of tin and other metal controls 1: (2 ~ 5);
Carbon/the silicon mol ratio in described porous polymer and silicon source is (2 ~ 10): 1;
Carbon/tin the mol ratio of described porous polymer and ashbury metal is (5 ~ 20): 1.
The preparation method of ashbury metal/silicon/carbon electrode material provided by the invention, compared with other cathode material preparation method, tool has the following advantages:
1) present invention process is simple, easy to operate, is conducive to suitability for industrialized production.
2) regulate and control the hydrolysis rate of silicon source on porous polymer surface, control dioxide deposition rate; By mechanical mixture ashbury metal, high temperature sintering obtains small-sized ashbury metal/silicon/carbon composite;
3) ashbury metal/silicon/carbon electrode material internal layer is material with carbon element, and centre is porous silicon, external sheath ashbury metal; This structure is not only conducive to electrical conductivity, and stops elementary silicon particle to come off in charge and discharge cycles process.
4) ashbury metal/silicon/carbon composite internal layer is carbon and the silicon of loose structure, and skin is good conductivity, constitutionally stable ashbury metal; This electrode material has height ratio capacity and long circulation life; Current density is 200mA/g, and circulate after 200 times, capacity is greater than 600mAh/g.
Embodiment
For summary of the invention of the present invention, Characteristic can be understood further, hereby lift following examples, and be described in detail as follows:
Embodiment 1
A kind of Composition Design of ashbury metal/silicon/carbon electrode material is:
Polyaniline, 0.01mol aniline polymerization product; Tetraethoxysilane, 0.03mol; Magnesium, 0.08mol; Gun-metal (SnCu
2, particle size < 50um), 0.005mol;
A kind of preparation method of ashbury metal/silicon/carbon electrode material: comprise the following steps:
1) polyaniline and the tetraethoxysilane that weigh certain mass are mixed in ethanol, stir 5h;
2) in step 1) slowly instill hydrous ethanol solution in mixture, control hydrous ethanol solution drop rate 1.5ml/min: controlled hydrolysis temperature 40 DEG C; Reaction time is 10h; Centrifugation, filtration washing, oven dry obtain polyaniline/silica;
3) step 2 of certain mass is weighed) product and magnesium metal mechanical mixture, then at 700 DEG C of inert atmosphere thermal reduction 4h; The mol ratio of silica and magnesium is 1: 2.5;
4) step 3) product immersion excessive hydrochloric acid, reaction 10h, filters, washs, dries, acquisition carbon/silicon composite;
5) step 4 of certain mass is weighed) product and gun-metal powder, inert atmosphere protection, mechanical mixture 15h, controls rotating speed 200 revs/min;
6) step 5 of certain mass is weighed) product, compressing tablet, inert atmosphere, high temperature 800 DEG C of standing 5h; Obtain ashbury metal/silicon/carbon electrode material;
The preparation and property test of negative pole; Using nickel tin-carbon-silicon electrode material as positive pole, lithium metal as negative pole, 1mol/LLiPF6 is dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC as electrolyte, and CELGARD2400 is that barrier film assembles button cell as barrier film.Land battery test system is adopted to carry out constant current charge-discharge test.Charging/discharging voltage scope is 0.02 ~ 1.5V, and current density is that after 200 circulations of 200mA/g. composite material, specific discharge capacity is greater than 600mAh/g.
Embodiment 2
A kind of Composition Design of ashbury metal/silicon/carbon electrode material is:
Polypyrrole, 0.01mol pyrroles's polymerizate; Tetraethoxysilane, 0.02mol; Magnesium, 0.06mol; Sn-ag alloy (SnAg
3, particle size < 50um), 0.003mol;
A kind of preparation method of ashbury metal/silicon/carbon electrode material: comprise the following steps:
1) polypyrrole and the tetraethoxysilane that weigh certain mass are mixed in ethanol, stir 5h;
2) in step 1) slow instillation water glycol solution in product, control hydrous ethanol solution drop rate 1ml/min: controlled hydrolysis temperature 50 C; Reaction time is 5h; Centrifugation, filtration washing, oven dry obtain polyaniline/silica;
3) step 2 of certain mass is weighed) product and magnesium metal mechanical mixture, then at 660 DEG C of inert atmosphere thermal reduction 6h; The mol ratio of silica and magnesium is 1: 3;
4) step 3) product immersion excessive hydrochloric acid, reaction 5h, filters, washs, dries, acquisition carbon/silicon composite;
5) step 4 of certain mass is weighed) product and sn-ag alloy powder, inert atmosphere protection, mechanical mixture 5h, controls rotating speed 300 revs/min;
6) step 5 of certain mass is weighed) product, compressing tablet, inert atmosphere, high temperature 900 DEG C of standing 4h; Obtain ashbury metal/silicon/carbon electrode material;
The preparation and property test of negative pole; Using nickel tin-carbon-silicon electrode material as positive pole, lithium metal as negative pole, 1mol/LLiPF6 is dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC as electrolyte, and CELGARD2400 is that barrier film assembles button cell as barrier film.Land battery test system is adopted to carry out constant current charge-discharge test.Charging/discharging voltage scope is 0.02 ~ 1.5V, and current density is that after 200 circulations of 200mA/g. composite material, specific discharge capacity is greater than 600mAh/g.
Embodiment 3
A kind of Composition Design of ashbury metal/silicon/carbon electrode material is:
Polypropylene is fine, the fine polymerizate of 0.01mol propylene; Silicon tetrachloride, 0.01mol; Magnesium, 0.03mol; Tin-nickel alloy (SnNi
3, particle size < 50um), 0.005mol;
Polyacetylene, 0.01mol acetylene polymerization product; Trichlorosilane, 0.01mol; Magnesium, 0.02mol; Tin ferroalloy (SnFe, particle size < 50um), 0.005mol;
A kind of implementation step of ashbury metal/silicon/carbon electrode material with embodiment 1,
The preparation and property test of negative pole; Using nickel tin-carbon-silicon electrode material as positive pole, lithium metal as negative pole, 1mol/LLiPF6 is dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC as electrolyte, and CELGARD2400 is that barrier film assembles button cell as barrier film.Land battery test system is adopted to carry out constant current charge-discharge test.Charging/discharging voltage scope is 0.02 ~ 1.5V, and current density is that after 200 circulations of 200mA/g. composite material, specific discharge capacity is greater than 600mAh/g.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (4)
1. the preparation method of ashbury metal/silicon/carbon electrode material, it is characterized in that: described ashbury metal/silicon/carbon electrode material take porous polymer as carrier, cvd silicon oxide, mechanical mixture magnesium, high-temperature hot reduction, acid treatment, filtering drying, again mechanical mixture ashbury metal, compressing tablet, high temperature sintering, obtain ashbury metal/silicon/carbon electrode material; Porous polymer is that polyacetylene, polypropylene are fine, the one of polyaniline, polypyrrole, phenolic resins; Ashbury metal is the one of nickeltin, signal bronze, ferro-tin alloy, silver-colored ashbury metal; Silicon source is the one of tetraethoxysilane, silicon tetrachloride, trichlorosilane; The preparation method of ashbury metal/silicon/carbon electrode material comprises the steps:
1) porous polymer and the silicon source that weigh certain mass are mixed in organic solvent, stir 1 ~ 10h;
Wherein, organic solvent is the one of methyl alcohol, ethanol, acetone, ethylene glycol, glycerol, oxolane;
2) in step 1) slowly instill hydrous ethanol solution in mixture, control hydrous ethanol solution drop rate 0.5 ~ 2ml/min: controlled hydrolysis temperature 25 ~ 70 DEG C; Reaction time is 2 ~ 40h; Centrifugation, filtration washing, oven dry obtain how empty polymer/silica;
Wherein, the volume ratio of water and ethanol is 0.05 ~ 0.95; The mol ratio (2 ~ 5) in water and silicon source: 1;
3) weigh the step 2 of certain mass) product and and magnesium metal mechanical mixture, then 600 ~ 800 DEG C of inert atmosphere thermal reduction 2 ~ 10h; The mol ratio of magnesium/silicon is (2 ~ 5): 1;
4) by step 3) product immersion excessive hydrochloric acid, reaction 2 ~ 40h, filters, washs, dries, acquisition carbon/silicon composite;
5) step 4 of certain mass is weighed) product and ashbury metal powder, inert atmosphere protection, mechanical mixture 1 ~ 20h, controls rotating speed 50-250 rev/min;
Wherein, ashbury metal powder particles size is less than 50 microns;
6) by step 5) product compressing tablet, inert atmosphere, high temperature 700 ~ 1200 DEG C leave standstill 1 ~ 10h; Obtain ashbury metal/silicon/carbon electrode material.
2. the preparation method of ashbury metal/silicon/carbon electrode material according to claim 1, is characterized in that: in ashbury metal, the mol ratio of tin and other metal controls 1: (2 ~ 5).
3. the preparation method of ashbury metal/silicon/carbon electrode material according to claim 1, is characterized in that: the carbon/silicon mol ratio in porous polymer and silicon source is (1 ~ 10): 1.
4. the preparation method of ashbury metal/silicon/carbon electrode material according to claim 1, is characterized in that: the carbon/tin mol ratio of porous polymer and ashbury metal is (5 ~ 20): 1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106848198A (en) * | 2017-02-22 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium battery cathode pole piece |
| CN109286014A (en) * | 2018-11-23 | 2019-01-29 | 浙江众泰汽车制造有限公司 | A kind of Si-C composite material and its preparation method and application that surface is modified |
| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN109997270A (en) * | 2016-11-29 | 2019-07-09 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
| CN110600719A (en) * | 2019-09-12 | 2019-12-20 | 河南电池研究院有限公司 | Porous silicon-carbon lithium ion battery cathode material with high rate performance and preparation method thereof |
| CN110707310A (en) * | 2019-10-29 | 2020-01-17 | 昆山宝创新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN112054171A (en) * | 2020-08-13 | 2020-12-08 | 利普同呈(江苏)新能源科技有限公司 | Carbon-silicon negative electrode material and preparation method thereof |
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| CN103238238A (en) * | 2010-10-22 | 2013-08-07 | 安普雷斯股份有限公司 | Composite structures containing high capacity porous active materials constrained in shells |
| US20130273246A1 (en) * | 2011-09-26 | 2013-10-17 | Safcell, Inc. | Efficient and simple method for metalorganic chemical vapor deposition |
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| CN103238238A (en) * | 2010-10-22 | 2013-08-07 | 安普雷斯股份有限公司 | Composite structures containing high capacity porous active materials constrained in shells |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109997270A (en) * | 2016-11-29 | 2019-07-09 | 三洋电机株式会社 | Non-aqueous electrolyte secondary battery |
| CN106848198A (en) * | 2017-02-22 | 2017-06-13 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium battery cathode pole piece |
| CN106848198B (en) * | 2017-02-22 | 2018-08-17 | 深圳市沃特玛电池有限公司 | A kind of preparation method of lithium battery cathode pole piece |
| CN109286014A (en) * | 2018-11-23 | 2019-01-29 | 浙江众泰汽车制造有限公司 | A kind of Si-C composite material and its preparation method and application that surface is modified |
| CN109728281A (en) * | 2018-12-31 | 2019-05-07 | 青岛农业大学 | A kind of preparation method of the modified SiOx electrode material in surface |
| CN110600719A (en) * | 2019-09-12 | 2019-12-20 | 河南电池研究院有限公司 | Porous silicon-carbon lithium ion battery cathode material with high rate performance and preparation method thereof |
| CN110707310A (en) * | 2019-10-29 | 2020-01-17 | 昆山宝创新能源科技有限公司 | Negative electrode material and preparation method and application thereof |
| CN112054171A (en) * | 2020-08-13 | 2020-12-08 | 利普同呈(江苏)新能源科技有限公司 | Carbon-silicon negative electrode material and preparation method thereof |
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