CN105470480B - A kind of preparation method of tin alloy/silicon/carbon electrode material - Google Patents
A kind of preparation method of tin alloy/silicon/carbon electrode material Download PDFInfo
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- CN105470480B CN105470480B CN201510848742.4A CN201510848742A CN105470480B CN 105470480 B CN105470480 B CN 105470480B CN 201510848742 A CN201510848742 A CN 201510848742A CN 105470480 B CN105470480 B CN 105470480B
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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 present invention relates to a kind of preparation method of tin alloy/silicon/carbon electrode material.This method is using porous polymer as carrier, cvd silicon oxide, mechanical mixture magnesium, high temperature thermal reduction, acid treatment, again filtering drying, mechanical mixture tin alloy, tabletting, high temperature sintering, obtains tin alloy/silicon/carbon electrode material；Porous polymer is polyacetylene, polypropylene is fine, polyaniline, polypyrrole, one kind of phenolic resin；Tin alloy is nickeltin, signal bronze, ferro-tin alloy, one kind of silver-tin alloy；Silicon source is tetraethyl orthosilicate, silicon tetrachloride, one kind of trichlorosilane.Tin alloy/silicon/carbon composite internal layer is the carbon and silicon of loose structure, and outer layer is good conductivity, constitutionally stable tin alloy；The electrode material has height ratio capacity and long circulation life；There is good application prospect in field of batteries.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material, and in particular to a kind of system of tin alloy/silicon/carbon electrode material
Preparation Method.
Background technology
Lithium ion battery negative material is the deciding factor for influenceing whole battery performance, security, cost etc.
One of.Commercial Li-ion batteries negative material graphite, its theoretical capacity is 372mAh/g, it is difficult to meet following Large Copacity, Gao Gong
The demand of rate, inexpensive electrochmical power source.Silicium cathode materials theory lithium storage content (4200mAh/g), rich reserves, it is a kind of non-
Often promising lithium ion battery negative material of future generation.But silicium cathode material Volume Changes in charge and discharge process are big
(volumetric expansion about 400%), electrode material is caused to occur rupture, efflorescence, structural breakdown etc. in cyclic process, and silicon
Electric conductivity is very low, causes that irreversible capacity is higher, cyclical stability is poor.How Volume Changes and the raising of silicon materials is buffered
Its electrical conductivity is the key for improving silicium cathode material electrochemical performance and realizing its commercial applications.Due to carbon material inherently
Commercialized lithium ion battery negative material, while cheap, stable performance, silico-carbo composite are always the heat researched and developed
Point and the selection of Industry Promotion.
Magasinski [Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J,
YushinG.Nat.Mater., 2010,9 (4)：353-358.] use heat treatment carbon black to obtain conducting matrix grain, then existed with CVD
Carbon blacksurface deposits nano-silicon and carbon, obtains Si-C composite material of the particle diameter at 15-30 μm.The composite material exhibits go out very
High capacity, excellent circulation and high rate performance.Conducting polymer has higher electrical conductivity, is the good carbon of electrode material
Source.In addition, polymer can provide good dispersiveness, help to prevent the generation of caking phenomenon.Conducting polymer has bullet
Property, effectively solve the problems, such as volumetric expansion of the electrode material in charge and discharge process, so as to improve the cyclical stability of battery and fill
Discharge performance.Kummer [Kummer M, Badillo JP, Schmitz A.J Electrochem Soc, 2014,161 (1)：
] etc. A40-A45. nano-silicon (n-Si) active material and the non-active material (polyaniline) as binding agent and buffer matrix are tied
Close and prepare n-Si/PANi.The material shows the capacity and cyclical stability higher than conventional anode material (graphite)；300 times
The theoretical specific capacity of the composite is maintained at more than 60% after circulation.Relative to softer conducting polymer, metal has very
The advantages that electric conductivity and mechanical strength for getting well, Volume Changes of the silicon in charge and discharge process can be more limited, while improve conduction
Property, contact of the isolation silicon materials with electrolyte, suppress the formation of SEI films.Wang [Wang X, Wen Z, Liu Y, Wu
X.Electrochim.Acta, 2009,54 (20)：4662-4667.] etc. use high-energy ball milling method, with lithium metal reduce SiO and
SnO, and a certain amount of graphite is added, prepare Si-Sn-Li4SiO4/ C composite.Reversible capacity is about first for the material
900mAh/g, the capability retention after 100 circulations is up to 79.2%.But metallic tin volume during charge and discharge cycles can also be sent out
Changing, and cause structure collapses, it is difficult to the effectively Volume Changes of containment silicon in the circulating cycle.
The content of the invention
Present invention aims at a kind of preparation method of tin alloy/silicon/carbon electrode material is provided, existing technology of preparing is overcome
The defects of, the cycle life of raising silicon electrode material.For achieving the above object, the technical scheme is that：With porous
Polymer is carrier, and cvd silicon oxide, mechanical mixture magnesium, high temperature thermal reduction, acid treatment, filtering drying, mechanical mixture tin closes again
Gold, tabletting, high temperature sintering, obtain tin alloy/silicon/carbon electrode material；Porous polymer be polyacetylene, polyacrylonitrile, polyaniline,
One kind of polypyrrole, phenolic resin；Tin alloy is nickeltin, signal bronze, ferro-tin alloy, one kind of silver-tin alloy；Silicon source
For tetraethyl orthosilicate, silicon tetrachloride, trichlorosilane one kind；The preparation method of tin alloy/silicon/carbon electrode material includes following step
Suddenly：
1) weigh the porous polymer of certain mass and silicon source is mixed in organic solvent, stir 1~10h；
2) hydrous ethanol solution, 0.5~2ml/ of control hydrous ethanol solution drop rate are slowly dropped into step 1) mixture
min：Control 25~70 DEG C of hydrolysis temperature；Reaction time is 2~40h；Centrifugation, filtration washing, drying obtain porous polymeric
Thing/silica；
3) the step 2) product and magnesium metal mechanical mixture of certain mass are weighed, then 600~800 DEG C of inert atmosphere heat are gone back
2~10h of original；The mol ratio of magnesium/silicon is (2~5): 1；
4) step 3) product is immersed into excessive hydrochloric acid, reacts 2~40h, filtering, washing, drying, obtain carbon/silicon composite wood
Material；
5) the step 4) product and tin alloy powder of certain mass, inert atmosphere protection, 1~20h of mechanical mixture, control are weighed
50-250 revs/min of rotating speed；
6) by 700~1200 DEG C of tabletting of step 5) product, inert atmosphere, high temperature 1~10h of standing；Acquisition tin alloy/silicon/
Carbon electrode material.
Organic solvent in described step 1 is methanol, ethanol, acetone, ethylene glycol, glycerine, one kind of tetrahydrofuran；
The volume ratio of water and ethanol in described step 2 is 0.05~0.95；The mol ratio of water and silicon source (2~5): 1；
Tin alloy powder particles size in described step 5 is less than 50 microns；
The mol ratio of tin and other metals is controlled 1 in described tin alloy: (2~5)；
Described porous polymer and carbon/silicon mol ratio of silicon source are (2~10): 1；
Described porous polymer and the carbon of tin alloy/tin mol ratio are (5~20): 1.
The preparation method of tin alloy/silicon/carbon electrode material provided by the invention, with other cathode material preparation method phases
Than having the following advantages that：
1) present invention process is simple and convenient to operate, and is advantageous to industrialized production.
2) regulate and control hydrolysis rate of the silicon source on porous polymer surface, control dioxide deposition rate；It is mixed by machinery
Tin alloy is closed, high temperature sintering obtains small-sized tin alloy/silicon/carbon composite；
3) tin alloy/silicon/carbon electrode material internal layer is carbon material, and centre is porous silicon, external sheath tin alloy；The structure
Electronics conduction is not only advantageous to, and prevents elementary silicon particle from being come off during charge and discharge cycles.
4) tin alloy/silicon/carbon composite internal layer is the carbon and silicon of loose structure, and outer layer is good conductivity, Stability Analysis of Structures
Tin alloy；The electrode material has height ratio capacity and long circulation life；Current density is 200mA/g, after circulating 200 times, is held
Amount is more than 600mAh/g.
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 tin alloy/silicon/carbon electrode material is：
Polyaniline, 0.01mol aniline polymerization products；Tetraethyl orthosilicate, 0.03mol；Magnesium, 0.08mol；Gun-metal
(SnCu2, particle size ＜ 50um), 0.005mol；
A kind of preparation method of tin alloy/silicon/carbon electrode material：Comprise the following steps：
1) weigh the polyaniline of certain mass and tetraethyl orthosilicate is mixed in ethanol, stir 5h；
2) hydrous ethanol solution, control hydrous ethanol solution drop rate 1.5ml/min are slowly dropped into step 1) mixture：
Control 40 DEG C of hydrolysis temperature；Reaction time is 10h；Centrifugation, filtration washing, drying obtain polyaniline/silica；
3) the step 2) product and magnesium metal mechanical mixture of certain mass are weighed, is then heat-treated in 700 DEG C of inert atmospheres
4h；The mol ratio of silica and magnesium is 1: 2.5；
4) step 3) product immerses excessive hydrochloric acid, reacts 10h, filtering, washing, drying, obtains carbon/silicon composite；
5) the step 4) product and gun-metal powder of certain mass, inert atmosphere protection, mechanical mixture 15h, control are weighed
200 revs/min of rotating speed；
6) the step 5) product of certain mass, 800 DEG C of tabletting, inert atmosphere, high temperature standing 5h are weighed；Acquisition tin alloy/
Silicon/carbon electrode material；
The preparation and performance test of negative pole；Using nickel tin-carbon-silicon electrode material as positive pole, lithium metal as negative pole,
1mol/L LiPF6 are dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC and are used as electrolyte, CELGARD 2400 be barrier film be used as every
Film assembles button cell.Constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope be 0.02~
1.5V, current density are more than 600mAh/g for specific discharge capacity after 200 circulations of 200mA/g. composites.
Embodiment 2
A kind of composition design of tin alloy/silicon/carbon electrode material is：
Polypyrrole, 0.01mol pyrroles's polymerizate；Tetraethyl orthosilicate, 0.02mol；Magnesium, 0.06mol；Sn-ag alloy
(SnAg3, particle size ＜ 50um), 0.003mol；
A kind of preparation method of tin alloy/silicon/carbon electrode material：Comprise the following steps：
1) weigh the polypyrrole of certain mass and tetraethyl orthosilicate is mixed in ethanol, stir 5h；
2) water glycol solution, control hydrous ethanol solution drop rate 1ml/min are slowly dropped into step 1) product：Control
50 DEG C of hydrolysis temperature processed；Reaction time is 5h；Centrifugation, filtration washing, drying obtain polyaniline/silica；
3) the step 2) product and magnesium metal mechanical mixture of certain mass are weighed, is then heat-treated in 660 DEG C of inert atmospheres
6h；The mol ratio of silica and magnesium is 1: 3；
4) step 3) product immerses excessive hydrochloric acid, reacts 5h, filtering, washing, drying, obtains carbon/silicon composite；
5) the step 4) product and sn-ag alloy powder of certain mass, inert atmosphere protection, mechanical mixture 5h, control turn are weighed
300 revs/min of speed；
6) the step 5) product of certain mass, 900 DEG C of tabletting, inert atmosphere, high temperature standing 4h are weighed；Acquisition tin alloy/
Silicon/carbon electrode material；
The preparation and performance test of negative pole；Using nickel tin-carbon-silicon electrode material as positive pole, lithium metal as negative pole,
1mol/L LiPF6 are dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC and are used as electrolyte, CELGARD 2400 be barrier film be used as every
Film assembles button cell.Constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope be 0.02~
1.5V, current density are more than 600mAh/g for specific discharge capacity after 200 circulations of 200mA/g. composites.
Embodiment 3
A kind of composition design of tin alloy/silicon/carbon electrode material is：
Polyacrylonitrile, 0.01mol acrylonitrile polymerization products；Silicon tetrachloride, 0.01mol；Magnesium, 0.03mol；Tin-nickel alloy
(SnNi3, particle size ＜ 50um), 0.005mol；
Polyacetylene, 0.01mol acetylene polymerization products；Trichlorosilane, 0.01mol；Magnesium, 0.02mol；Tin ferroalloy (SnFe,
Particle size ＜ 50um), 0.005mol；
A kind of implementation steps of tin alloy/silicon/carbon electrode material with embodiment 1,
The preparation and performance test of negative pole；Using nickel tin-carbon-silicon electrode material as positive pole, lithium metal as negative pole,
1mol/L LiPF6 are dissolved in EC: DMC: EMC (1: 1: 1)+5%FEC and are used as electrolyte, CELGARD 2400 be barrier film be used as every
Film assembles button cell.Constant current charge-discharge test is carried out using Land battery test systems.Charging/discharging voltage scope be 0.02~
1.5V, current density are more than 600mAh/g for specific discharge capacity after 200 circulations of 200mA/g. composites.
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 (4)
- A kind of 1. preparation method of tin alloy/silicon/carbon electrode material, it is characterised in that：Described tin alloy/silicon/carbon electrode material Material is using porous polymer as carrier, cvd silicon oxide, mechanical mixture magnesium, high temperature thermal reduction, acid treatment, again filtering drying, machinery Tin alloy, tabletting, high temperature sintering are mixed, obtains tin alloy/silicon/carbon electrode material；Porous polymer is polyacetylene, polypropylene Nitrile, polyaniline, polypyrrole, one kind of phenolic resin；Tin alloy is nickeltin, signal bronze, ferro-tin alloy, silver-tin alloy It is a kind of；Silicon source is tetraethyl orthosilicate, silicon tetrachloride, one kind of trichlorosilane；The preparation method of tin alloy/silicon/carbon electrode material Comprise the following steps：1) weigh the porous polymer of certain mass and silicon source is mixed in organic solvent, stir 1~10h；Wherein, organic solvent is methanol, ethanol, acetone, ethylene glycol, glycerine, one kind of tetrahydrofuran；2) hydrous ethanol solution, 0.5~2ml/min of control hydrous ethanol solution drop rate are slowly dropped into step 1) mixture： Control 25~70 DEG C of hydrolysis temperature；Reaction time is 2~40h；Centrifugation, filtration washing, drying obtain porous polymer/oxygen SiClx；Wherein, the volume ratio of water and ethanol is 0.05~0.95；The mol ratio of water and silicon source (2~5): 1；3) the step 2) product and magnesium metal mechanical mixture of certain mass are weighed, then 600~800 DEG C of inert atmosphere thermal reductions 2 ~10h；The mol ratio of magnesium/silicon is (2~5): 1；4) step 3) product is immersed into excessive hydrochloric acid, reacts 2~40h, filtering, washing, drying, obtain carbon/silicon composite；5) the step 4) product and tin alloy powder of certain mass are weighed, inert atmosphere protection, 1~20h of mechanical mixture, controls rotating speed 50-250 revs/min；Wherein, tin alloy powder particles size is less than 50 microns；6) by 700~1200 DEG C of tabletting of step 5) product, inert atmosphere, high temperature 1~10h of standing；Obtain tin alloy/silicon/carbon electricity Pole material.
- 2. the preparation method of tin alloy/silicon/carbon electrode material according to claim 1, it is characterised in that：In tin alloy tin with The mol ratio of other metals is controlled 1: (2~5).
- 3. the preparation method of tin alloy/silicon/carbon electrode material according to claim 1, it is characterised in that：Porous polymer with Carbon/silicon mol ratio of silicon source is (1~10): 1.
- 4. the preparation method of tin alloy/silicon/carbon electrode material according to claim 1, it is characterised in that：Porous polymer with The carbon of tin alloy/tin mol ratio is (5~20): 1.
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| US20200067094A1 (en) * | 2016-11-29 | 2020-02-27 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| 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 |
| CN109728281B (en) * | 2018-12-31 | 2021-10-12 | 青岛农业大学 | Preparation method of surface modified SiOx electrode material |
| CN110600719B (en) * | 2019-09-12 | 2021-10-22 | 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 |
| CN110707310B (en) * | 2019-10-29 | 2021-01-12 | 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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| CN102130323A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
| 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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| 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 |
| CN102130323A (en) * | 2011-02-12 | 2011-07-20 | 中南大学 | Lithium ion battery film cathode containing porous polymer elastomer and preparation method thereof |
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