CN105355888A - Preparing method for nickel tin-carbon-silicon electrode material - Google Patents
Preparing method for nickel tin-carbon-silicon electrode material Download PDFInfo
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- CN105355888A CN105355888A CN201510848744.3A CN201510848744A CN105355888A CN 105355888 A CN105355888 A CN 105355888A CN 201510848744 A CN201510848744 A CN 201510848744A CN 105355888 A CN105355888 A CN 105355888A
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- H—ELECTRICITY
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- 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
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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
- H01M4/381—Alkaline or alkaline earth metals elements
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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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- 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 preparing method for a nickel tin-carbon-silicon electrode material. According to the material, silicon oxide with the high specific surface area is used as a raw material, mechanically mixed with magnesium, reduced in a high temperature thermal mode, treated in an acid mode, and coated with a conducting polymer, nickel oxide and tin oxide are deposited, and tabletting and high-temperature thermal reducing are carried out, so that the nickel tin-carbon-silicon electrode material is obtained; the specific surface area of silicon oxide is larger than 700 m<2>/g, and silicon oxide is one of silicon oxide nanometer powder, silicon oxide nanospheres, silicon oxide SBA-15, silicon oxide MCM-41 and silicon oxide KIT-6; the conducting polymer is one of polyaniline, polypyrrole, polythiophene and polyacetylene; the molar ratio of silicon oxide to magnesium is 1:(2-4), the molar ratio of silicon oxide to the conducting polymer precursor is 1:(1-5), the molar ratio of nickel oxide to the conducting polymer precursor is 1:(1-20), and the molar ratio of nickel oxide to tin oxide is 3:(1-8). The composite material has the advantages of being stable in structure and good in conductivity, having high specific capacity and excellent cycle performance when being used in a negative pole of a lithium battery, and having a good application prospect in the field of the batteries.
Description
Technical field
The present invention relates to a kind of preparation method of electrode material, be specifically related to the preparation method of a kind of nickel tin-carbon-silicon electrode material.
Background technology
Energy problem is the key issue being related to whole world sustainable development, seeks and develops the important state basic policy that alternative secondary energy sources are countries in the world.Lithium ion battery is the new generation of green high-energy battery that gets up of fast development during the last ten years recently, have voltage high, than can high, the advantage such as cycle period is long, environmental pollution is little, have become the first-selection of secondary energy sources.Lithium ion battery is widely used in mobile phone, notebook computer, portable power tool and electric automobile etc., therefore has broad application prospects.
Compared with lithium ion battery miscellaneous part, lithium ion cell positive and negative material are as the deciding factor affecting whole battery performance, fail safe, cost etc., and its development receives extensive concern.Now widely used commercial Li-ion batteries negative material is mainly graphite, and its theoretical capacity is 372mAh/g, and the demand of the chemical power source of the following Large Copacity of very difficult adaptation, high power, low cost, as electric automobile and peak load regulation network energy storage etc.Silicon based anode material has high theoretical lithium storage content (4200mAh/g), rich reserves, advantage of lower cost, the advantages such as environmentally safe, is a kind of very promising lithium ion battery negative material of future generation.But silicon based anode material in removal lithium embedded process with larger change in volume (volumetric expansion about 400%), cause the shortcomings such as battery electrode material in cyclic process can break, efflorescence, structural breakdown, add that 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 silicon based anode material chemical property He realize its commercial applications.
[YoshioM, WangH, the FukudaK such as Yoshio, UmenoT, DimovN, OgumiZJ.Electrochem.Soc., 2002,149:A1598-A1603.] be carbon source with benzene, the hud typed Si-C composite material that adopted chemical vapour deposition (CVD) (CVD) legal system standby.This material capacity after 20 circulations is still stabilized in more than 950mAh/g.Kim etc. [KimH, HanB, ChooJ, ChoJ.Angew.Chem.Int.Ed., 2008,47 (52): 10151-10154.] are with naphthalene sodium, SiCl
4, butyl lithium and SiO
2for raw material gel solidification, after further carbonization, etching, obtain the Si-C composite material with three-dimensional porous structure.This material list reveals excellent cycle performance and high rate performance, and the reversible capacity of 0.2C multiplying power is 2820mAh/g, and the capability retention after 100 circulations is 99%, even if under 3C multiplying power, still can release the reversible capacity of 2158mAh/g.
Magasinski [MagasinskiA, DixonP, HertzbergB, KvitA, AyalaJ, YushinG.Nat.Mater., 2010,9 (4): 353-358.] etc. has prepared Si-C composite material by two step chemical vapour deposition (CVD)s; First heat treatment carbon black obtains conducting matrix grain, then adopts CVD at depositing nano silicon grain above, finally by CVD deposit carbon and granulation, obtains particle diameter at the Si-C composite material of 15-30 μm.This dendritic carbon skeleton is that lithium ion provides freely unimpeded conduction pathway, and inner unordered loose structure is that the volumetric expansion of silicon grain provides space, and therefore this composite material exhibits goes out very high capacity, excellent circulation and high rate performance.Su Fabing [ZhangZL, WangYH, RenWF, TanQQ, SuFB.Angew.Chem.Int.Ed.2014,53:5165-5169.] etc. use for reference silicone monomer industry process, with industrial silica fume and chloromethanes for raw material, reacted by Rochow, utilize multiple copper-based catalysts to prepare porous silicon/carbon composite material in a mild condition.This material keeps the capacity of 1000mAh/g after 100 circulations.
Undeniable, the silicon/carbon composite of high-specific surface area, loose structure improves high rate performance and the cycle performance of silicon electrode material.But there is expansion and reduce in silicon/carbon volume in charge and discharge process, active material still can be caused to come off from electrode slice.
Summary of the invention
The object of the invention is to provide a kind of nickel tin-carbon-silicon electrode material preparation method, overcomes the defect of existing technology of preparing, the cycle life of silicon electrode material.For achieving the above object, technical scheme of the present invention is: with the silica of high-specific surface area for raw material, mechanical mixture magnesium, high-temperature hot reduction, acid treatment, again coated with conductive polymer, deposited oxide nickel and tin oxide, compressing tablet, high-temperature hot are reduced, and obtain nickel tin-carbon-silicon electrode material; The specific area of silica is greater than 700m
2/ g is the one of monox nanometer powder, monox nanometer ball, silica SBA-15, silica MCM-41, silica KIT-6; Conducting polymer is the one of polyaniline, polypyrrole, polythiophene, polyacetylene; The mol ratio of silica and magnesium is 1: (2 ~ 4), and the mol ratio of silica and conducting polymer presoma is 1: (1 ~ 5), and the mol ratio of nickel oxide and conducting polymer presoma is 1: (1 ~ 20); The mol ratio of nickel oxide and tin oxide is 3: (1 ~ 8); The preparation method of nickel tin-carbon-silicon electrode material comprises the steps:
1) silica and magnesium metal mechanical mixture, then 600 ~ 800 DEG C of inert atmosphere thermal reduction 2 ~ 10h of certain mass are weighed;
2) step 1) product immersion excessive hydrochloric acid, reaction 2 ~ 40h, filters, washs, dries, acquisition porous silicon;
3) by step 2) product and polymer precursor be mixed in the organic solution of hydrochloric acid, adds surfactant and the 1 ~ 10h that stirs;
4) in step 3) mixture in the hydrochloric acid solution of slow instillation persulfuric acid thing, rate of addition controls at 0.5 ~ 4ml/min; Control reaction temperature 0 ~ 5 DEG C, reaction time 5 ~ 30h; Agitation and filtration, oven dry etc., obtain polymer/silicon composite;
5) soluble nickel salt of certain mass, pink salt and step 4 is weighed) product is mixed in hydrochloric acid; Add surfactant to stir 1 ~ 10h: slowly instill sodium hydroxide solution, control solution pH value 5 ~ 9, reaction time 1 ~ 10h; Agitation and filtration, oven dry etc., obtain polymer/silicon/nickel oxide/tin oxide composite material;
6) step 5) product compressing tablet, inert atmosphere, 400 ~ 900 DEG C of heating 1 ~ 5h; Obtain nickel tin-carbon-silicon electrode material.In hydrochloric acid in described step 3, the mass fraction of HCl is 1 ~ 15%; Hydrochloric acid and organic volume ratio are 0.1 ~ 0.8; Organic substance is the one of methyl alcohol, ethanol, ethylene glycol, glycerol, oxolane;
Persulfuric acid thing in described step 4 is the one of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate; Persulfuric acid thing and polybenzazole precursor body mass ratio control 1: (1 ~ 1.35);
In described step 5, soluble nickel salt is the one of nickel acetate, nickel nitrate, protochloride nickel; Solubility pink salt is the one of nitric acid tin, stannous chloride, nitric acid tin;
The preparation method of nickel tin-carbon-silicon 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) specific area, the SOLUTION PROPERTIES of silica is regulated and controled, mixing rate, reaction temperature etc.; Nickel tin-carbon-silicon electrode material that acquisition mixes, loose structure, size are little;
3) nickel tin-carbon-silicon electrode material inner layer is the silicon materials of porous, and centre is material with carbon element, external sheath nickeltin; This structure is not only conducive to electrical conductivity, and stops silicon/material with carbon element to come off in charge and discharge cycles process.
4) nickel tin-carbon-silicon electrode material inner layer carbon silicon porous, outer nickeltin Stability Analysis of Structures, prevent material structural change because of volumetric expansion, 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, be described in detail as follows:
Embodiment 1
A kind of Composition Design of nickel tin-carbon-silicon electrode material is:
Silica (MCM-41, specific area > 700m
2/ g), 0.05mol; Magnesium, 0.12mol; Aniline, 0.15mol; Nickel nitrate, 0.015mol; Stannous chloride, 0.006mol;
A kind of preparation method of nickel tin-carbon-silicon electrode material: comprise the following steps:
1) silica MCM-41 and magnesium metal mechanical mixture, then 700 DEG C of inert atmosphere thermal reduction 4h of certain mass are weighed;
2) step 1) product immersion excessive hydrochloric acid, reaction 10h, filters, washs, dries, acquisition porous silicon;
3) by step 2) product and polymer precursor be mixed in hydrochloric acid alcoholic solution, add surfactant softex kw and stir 5h: wherein: in hydrochloric acid, the mass fraction of HCl is 5%; The volume ratio of hydrochloric acid and alcohol is 0.4;
4) in step 3) mixture in the hydrochloric acid solution of slow instillation sodium peroxydisulfate, rate of addition controls at 0.5 ~ 4ml/min; Control reaction temperature 0 DEG C, reaction time 5h; Agitation and filtration, oven dry etc., obtain polyaniline/silicon composite; Sodium peroxydisulfate and aniline mass ratio control 1: 1.25;
5) nickel nitrate of certain mass, stannous chloride and and step 4 is weighed) product is mixed in hydrochloric acid; Add surfactant softex kw to stir 5h: slowly instill sodium hydroxide solution, control solution pH value 5 ~ 9, reaction time 6h; Agitation and filtration, oven dry etc., obtain polyaniline/silicon/nickel oxide/tin oxide composite material;
6) step 5) product compressing tablet, inert atmosphere, 600 DEG C of heating 4h; Obtain nickel tin-carbon-silicon 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 nickel tin-carbon-silicon electrode material is:
Silica (SBA-15, specific area > 700m
2/ g), 0.05mol; Magnesium, 0.15mol; Pyrroles, 0.2mol; Nickel acetate, 0.02mol; Stannous chloride, 0.02mol;
A kind of preparation method of nickel tin-carbon-silicon electrode material: comprise the following steps:
1) silica SBA-15 and magnesium metal mechanical mixture, then 660 DEG C of inert atmosphere thermal reduction 6h of certain mass are weighed;
2) by step 1) product immersion excessive hydrochloric acid, reaction 5h, filters, washs, dries, acquisition porous silicon;
3) step 2 of certain mass is weighed) product and pyrroles be mixed in the tetrahydrofuran solution of hydrochloric acid, adds surfactant polyvinylpyrrolidone and the 3h that stirs: wherein: in hydrochloric acid, the mass fraction of HCl is 3.5%; The volume ratio of hydrochloric acid and oxolane is 0.6;
4) in step 3) mixture in the hydrochloric acid solution of slow instillation ammonium persulfate, rate of addition controls at 0.5 ~ 4ml/min; Control reaction temperature 0 DEG C, reaction time 8h; Agitation and filtration, oven dry etc., obtain polypyrrole/silicon composite; Ammonium persulfate and pyrroles's mass ratio control 1: 1.3;
5) weigh the nickel acetate of certain mass, stannous chloride and step 4) product be mixed in hydrochloric acid; Add surfactant polyvinylpyrrolidone and stir 5h: slowly instill sodium hydroxide solution, control solution pH value 5 ~ 9, reaction time 6h; Agitation and filtration, oven dry etc., obtain polypyrrole/silicon/nickel oxide/tin oxide composite material;
6) step 5) product compressing tablet, inert atmosphere, 500 DEG C of heating 5h; Obtain nickel tin-carbon-silicon 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 nickel tin-carbon-silicon electrode material is:
Silica (nanosphere, specific area > 700m
2/ g), 0.05mol; Magnesium, 0.1mol; Thiophene, 0.1mol; Protochloride nickel, 0.005mol; Tin acetate, 0.01mol;
Silica (nano powder, specific area > 700m
2/ g), 0.05mol; Magnesium, 0.2mol; Pyrroles, 0.25mol; Nickel acetate, 0.05mol; Tin acetate, 0.016mol;
A kind of preparation method of nickel tin-carbon-silicon electrode material is identical with example 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 (1)
1. the preparation method of nickel tin-carbon-silicon electrode material, it is characterized in that: with the silica of high-specific surface area for raw material, mechanical mixture magnesium, high-temperature hot reduction, acid treatment, again coated with conductive polymer, deposited oxide nickel and tin oxide, compressing tablet, high-temperature hot are reduced, and obtain nickel tin-carbon-silicon electrode material; The specific area of silica is greater than 700m
2/ g is the one of monox nanometer powder, monox nanometer ball, silica SBA-15, silica MCM-41, silica KIT-6; Conducting polymer is the one of polyaniline, polypyrrole, polythiophene, polyacetylene; The mol ratio of silica and magnesium is 1: (2 ~ 4), and the mol ratio of silica and conducting polymer presoma is 1: (1 ~ 5), and the mol ratio of nickel oxide and conducting polymer presoma is 1: (1 ~ 20); The mol ratio of nickel oxide and tin oxide is 3: (1 ~ 8); The preparation method of nickel tin-carbon-silicon electrode material comprises the steps:
1) silica and magnesium metal mechanical mixture, then 600 ~ 800 DEG C of inert atmosphere thermal reduction 2 ~ 10h of certain mass are weighed;
2) by step 1) product immersion excessive hydrochloric acid, reaction 2 ~ 40h, filters, washs, dries, acquisition porous silicon;
3) by step 2) product and polymer precursor be mixed in the organic solution of hydrochloric acid, adds surfactant and the 1 ~ 10h that stirs;
Wherein: in hydrochloric acid, the mass fraction of HCl is 1 ~ 15%; Hydrochloric acid and organic volume ratio are 0.1 ~ 0.8; Organic substance is the one of methyl alcohol, ethanol, ethylene glycol, glycerol, oxolane;
4) in step 3) mixture in the hydrochloric acid solution of slow instillation persulfuric acid thing, rate of addition controls at 0.5 ~ 4ml/min; Control reaction temperature 0 ~ 5 DEG C, reaction time 5 ~ 30h; Agitation and filtration, oven dry etc., obtain polymer/silicon composite;
Wherein, persulfuric acid thing is the one of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate; Persulfuric acid thing and polybenzazole precursor body mass ratio control 1: (1 ~ 1.35);
5) soluble nickel salt of certain mass, pink salt and step 4 is weighed) product is mixed in hydrochloric acid; Add surfactant to stir 1 ~ 10h: slowly instill sodium hydroxide solution, control solution pH value 5 ~ 9, reaction time 1 ~ 10h; Agitation and filtration, oven dry etc., obtain polymer/silicon/nickel oxide/tin oxide composite material;
Wherein, soluble nickel salt is the one of nickel acetate, nickel nitrate, protochloride nickel; Solubility pink salt is the one of nitric acid tin, stannous chloride, nitric acid tin;
6) step 5) product compressing tablet, inert atmosphere, 400 ~ 900 DEG C of heating 1 ~ 5h; Obtain nickel tin-carbon-silicon electrode material.
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| 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 |
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| CN103633305A (en) * | 2013-12-10 | 2014-03-12 | 苏州宇豪纳米材料有限公司 | Silicon composite anode material of lithium ion battery and preparation method of silicon composite anode material |
| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
| CN104681798A (en) * | 2015-02-12 | 2015-06-03 | 中南大学 | Method for preparing silicon-based composite anode material of lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103633305A (en) * | 2013-12-10 | 2014-03-12 | 苏州宇豪纳米材料有限公司 | Silicon composite anode material of lithium ion battery and preparation method of silicon composite anode material |
| CN104466185A (en) * | 2014-11-12 | 2015-03-25 | 中国科学院深圳先进技术研究院 | Silicon/carbon negative electrode composite material and preparation method thereof as well as lithium ion battery and negative electrode thereof |
| CN104681798A (en) * | 2015-02-12 | 2015-06-03 | 中南大学 | Method for preparing silicon-based composite anode material of lithium ion battery |
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| 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 |
| 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 |
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Inventor after: Zhu Yuying Inventor after: Yao Luxi Inventor after: Fan Meiqiang Inventor after: Chang Jiasong Inventor after: Song Lutao Inventor after: Chen Zhe Inventor before: Yao Luxi Inventor before: Fan Meiqiang Inventor before: Chang Jiasong Inventor before: Song Lutao Inventor before: Chen Zhe |
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