CN105355888B - A kind of preparation method of nickel tin carbon-silicon electrodes material - Google Patents

A kind of preparation method of nickel tin carbon-silicon electrodes material Download PDF

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CN105355888B
CN105355888B CN201510848744.3A CN201510848744A CN105355888B CN 105355888 B CN105355888 B CN 105355888B CN 201510848744 A CN201510848744 A CN 201510848744A CN 105355888 B CN105355888 B CN 105355888B
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nickel
silica
tin
silicon
carbon
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CN105355888A (en
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朱宇莹
姚炉锡
范美强
常珈菘
宋璐涛
陈哲
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China Jiliang University
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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
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/381—Alkaline or alkaline earth metals elements
    • 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
    • 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 nickel tin carbon-silicon electrodes material.The material is using the silica of high-specific surface area as raw material, mechanical mixture magnesium, high temperature thermal reduction, again acid treatment, coated with conductive polymer, deposited oxide nickel and tin oxide, tabletting, high temperature thermal reduction, obtains nickel tin carbon-silicon electrodes material；The specific surface area of silica is more than 700m2/ g, to aoxidize silicon nano power, monox nanometer ball, silica SBA 15, silica MCM 41, silica KIT 6 one kind；Conducting polymer is polyaniline, polypyrrole, polythiophene, one kind of polyacetylene；The mol ratio of silica and magnesium is 1: the mol ratio of (2~4), silica and conducting polymer presoma is 1: the mol ratio of (1~5), nickel oxide and conducting polymer presoma is 1: (1~20)；The mol ratio of nickel oxide and tin oxide is 3: (1~8).The composite has the advantages that Stability Analysis of Structures, good conductivity, during for cathode of lithium battery, has very high specific capacity and excellent cycle performance, has good application prospect in field of batteries.

Description

A kind of preparation method of nickel tin-carbon-silicon electrode material
Technical field
The present invention relates to a kind of preparation method of electrode material, and in particular to a kind of preparation of nickel tin-carbon-silicon electrode material Method.
Background technology
Energy problem is the key issue for being related to whole world sustainable development, seeks and develops alternative secondary energy sources It is the important state basic policy of countries in the world.Lithium ion battery is the new generation of green high energy electricity that fast development is got up during the last ten years recently Pond, there is the advantages such as voltage is high, higher than energy, cycle period is long, environmental pollution is small, have become the first choice of secondary energy sources.Lithium from Sub- battery is widely used in mobile phone, notebook computer, portable power tool and electric automobile etc., therefore with wide Application prospect.
Compared with lithium ion battery miscellaneous part, lithium ion cell positive and negative material are electrochemical as whole battery is influenceed The deciding factor of performance, security, cost etc. is learned, its development receives extensive concern.Now widely used business lithium from Sub- cell negative electrode material is mainly graphite, and its theoretical capacity is 372mAh/g, it is difficult to adapt to following Large Copacity, high power, it is low into The demand of this electrochmical power source, such as electric automobile and peak load regulation network energy storage.Silicon based anode material has high theoretical storage lithium Capacity (4200mAh/g), rich reserves, advantage of lower cost, it is environmentally safe the advantages that, be a kind of very promising Lithium ion battery negative material of future generation.But silicon based anode material is during removal lithium embedded with larger Volume Changes (body About 400%) product expansion, the shortcomings of causing battery rupture, efflorescence, structural breakdown can occur for electrode material in cyclic process, adds The electric conductivity of upper silicon is very low, causes that irreversible capacity is higher, cyclical stability is poor.How the Volume Changes of silicon materials are buffered It is to improve silicon based anode material chemical property and realize the key of its commercial applications with its electrical conductivity is improved.
[Yoshio M, Wang H, Fukuda K, Umeno T, Dimov N, the Ogumi Z such as Yoshio J.Electrochem.Soc., 2002,149：A1598-A1603.] using benzene as carbon source, using chemical vapor deposition (CVD) legal system For hud typed Si-C composite material.Material capacity after 20 circulations is still stablized in more than 950mAh/g.[the Kim such as Kim H, Han B, Choo J, Cho J.Angew.Chem.Int.Ed., 2008,47 (52)：10151-10154.] with naphthalene sodium, SiCl4, butyl lithium and SiO2For raw material gel solidification, further obtain having the silicon-carbon of three-dimensional porous structure to answer after carbonization, etching Condensation material.The material shows excellent cycle performance and high rate performance, and the reversible capacity of 0.2C multiplying powers is 2 820mAh/g, Capability retention after 100 circulations is 99%, under 3C multiplying powers, remains to release 2 158mAh/g reversible capacity.
Magasinski [Magasinski A, Dixon P, Hertzberg B, Kvit A, Ayala J, YushinG.Nat.Mater., 2010,9 (4)：353-358.] etc. be prepared for silicon-carbon composite wood by two step chemical vapor depositions Material；Heat treatment carbon black first obtains conducting matrix grain, then silicon nanoparticle is deposited above using CVD, finally by CVD deposition carbon And be granulated, obtain Si-C composite material of the particle diameter at 15-30 μm.This dendritic carbon skeleton provides certainly for lithium ion By unimpeded conduction pathway, and internal unordered loose structure provides space for the volumetric expansion of silicon grain, therefore this is compound Material shows very high capacity, excellent circulation and high rate performance.Su Fabing [Zhang Z L, Wang Y H, Ren W F, Tan Q Q, Su F B.Angew.Chem.Int.Ed.2014,53：5165-5169.] etc. use for reference silicone monomer industry process, Using industrial silica fume and chloromethanes as raw material, reacted, prepared in a mild condition using a variety of copper-based catalysts more by Rochow Hole silicon/carbon composite.The material keeps 1000mAh/g capacity after 100 circulations.
Undeniably, high-specific surface area, silicon/carbon composite of loose structure improve the high rate performance of silicon electrode material And cycle performance.But there is expansion and reduce in silicon/carbon volume in charge and discharge process, can still cause active material from electrode slice On come off.
The content of the invention
Present invention aims at a kind of nickel tin-carbon-silicon electrode material preparation method is provided, lacking for existing technology of preparing is overcome Fall into, the cycle life of silicon electrode material.For achieving the above object, the technical scheme is that：With high-specific surface area Silica is raw material, mechanical mixture magnesium, high temperature thermal reduction, again acid treatment, coated with conductive polymer, deposited oxide nickel and oxidation Tin, tabletting, high temperature thermal reduction, obtain nickel tin-carbon-silicon electrode material；The specific surface area of silica is more than 700m2/ g, for oxidation Silicon nano power, monox nanometer ball, silica SBA-15, silica MCM-41, silica KIT-6 one kind；Conducting polymer For polyaniline, polypyrrole, polythiophene, polyacetylene one kind；The mol ratio of silica and magnesium is 1: (2~4), silica and conduction The mol ratio of polymer precursor is 1: the mol ratio of (1~5), nickel oxide and conducting polymer presoma is 1: (1~20)；Oxygen The mol ratio for changing nickel and tin oxide is 3: (1~8)；The preparation method of nickel tin-carbon-silicon electrode material comprises the following steps：
1) silica and magnesium metal mechanical mixture of certain mass are weighed, then 600~800 DEG C of inert atmosphere thermal reductions 2 ~10h；
2) step 1) product immerses excessive hydrochloric acid, reacts 2~40h, filtering, washing, drying, obtains porous silicon；
3) step 2) product and polymer precursor are mixed in the organic solution of hydrochloric acid, surfactant is added and stirs Uniform 1~10h；
4) be slowly dropped into the hydrochloric acid solution of persulfuric acid thing in the mixture of step 3), rate of addition control 0.5~ 4ml/min；0~5 DEG C of controlling reaction temperature, 5~30h of reaction time；Agitation and filtration, drying etc., obtain polymer/silicon composite wood Material；
5) soluble nickel salt, pink salt and the step 4) product for weighing certain mass are mixed in hydrochloric acid；Add surfactant Stir 1~10h：It is slowly dropped into sodium hydroxide solution, control solution pH value 5~9,1~10h of reaction time；Agitation and filtration, Drying etc., obtain polymer/silicon/nickel oxide/oxidation tin composite material；
6) step 5) product tabletting, inert atmosphere, 400~900 DEG C of 1~5h of heating；Obtain nickel tin-carbon-silicon electrode material Material.HCl mass fraction is 1~15% in hydrochloric acid in described step 3；The volume ratio of hydrochloric acid and organic matter be 0.1~ 0.8；Organic matter is methanol, ethanol, ethylene glycol, glycerine, one kind of tetrahydrofuran；
Persulfuric acid thing in described step 4 is one kind of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；Persulfuric acid thing with Polybenzazole precursor body mass ratio is controlled 1: (1~1.35)；
Soluble nickel salt is nickel acetate, nickel nitrate, one kind of protochloride nickel in described step 5；Soluble pink salt is nitre Sour tin, stannous chloride, one kind of nitric acid tin；
The preparation method of nickel tin-carbon-silicon electrode material provided by the invention, compared with other cathode material preparation methods, Have the following advantages that：
1) present invention process is simple and convenient to operate, and is advantageous to industrialized production.
2) specific surface area, the SOLUTION PROPERTIES, mixing rate, reaction temperature etc. of silica are regulated and controled；It is well mixed, is porous The small nickel tin-carbon-silicon electrode material of structure and size；
3) nickel tin-carbon-silicon electrode material inner layer is porous silicon materials, and centre is carbon material, external sheath nickeltin； The structure is not only advantageous to electronics conduction, and prevents silicon/carbon material from being come off during charge and discharge cycles.
4) nickel tin-carbon-silicon electrode material inner layer carbon silicon is porous, outer layer nickeltin Stability Analysis of Structures, prevents material because of volume Expansion and structure change, material have 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, describe in detail such as Under：
Embodiment 1
A kind of composition design of nickel tin-carbon-silicon electrode material is：
Silica (MCM-41, specific surface area ＞ 700m2/ g), 0.05mol；Magnesium, 0.12mol；Aniline, 0.15mol；Nitric acid Nickel, 0.015mol；Stannous chloride, 0.006mol；
A kind of preparation method of nickel tin-carbon-silicon electrode material：Comprise the following steps：
1) the silica MCM-41 and magnesium metal mechanical mixture of certain mass are weighed, then 700 DEG C of inert atmosphere thermal reductions 4h；
2) step 1) product immerses excessive hydrochloric acid, reacts 10h, filtering, washing, drying, obtains porous silicon；
3) step 2) product and polymer precursor are mixed in the alcoholic solution of hydrochloric acid, add surfactant 16 Alkyl trimethyl ammonium bromide simultaneously stirs 5h：Wherein：HCl mass fraction is 5% in hydrochloric acid；The volume ratio of hydrochloric acid and alcohol is 0.4；
4) be slowly dropped into the hydrochloric acid solution of sodium peroxydisulfate in the mixture of step 3), rate of addition control 0.5~ 4ml/min；0 DEG C of controlling reaction temperature, reaction time 5h；Agitation and filtration, drying etc., obtain polyaniline/silicon composite；Over cure Sour sodium is controlled 1: 1.25 with aniline mass ratio；
5) nickel nitrate of certain mass, stannous chloride are weighed and is mixed in hydrochloric acid with step 4) product；Add surface-active Agent cetyl trimethylammonium bromide stirs 5h：It is slowly dropped into sodium hydroxide solution, control solution pH value 5~9, during reaction Between 6h；Agitation and filtration, drying etc., obtain polyaniline/silicon/nickel oxide/oxidation tin composite material；
6) step 5) product tabletting, inert atmosphere, 600 DEG C of heating 4h；Obtain nickel tin-carbon-silicon 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 nickel tin-carbon-silicon electrode material is：
Silica (SBA-15, specific surface area ＞ 700m2/ g), 0.05mol；Magnesium, 0.15mol；Pyrroles, 0.2mol；Acetic acid Nickel, 0.02mol；Stannous chloride, 0.02mol；
A kind of preparation method of nickel tin-carbon-silicon electrode material：Comprise the following steps：
1) the silica SBA-15 and magnesium metal mechanical mixture of certain mass are weighed, then 660 DEG C of inert atmosphere thermal reductions 6h；
2) step 1) product is immersed into excessive hydrochloric acid, reacts 5h, filtering, washing, drying, obtain porous silicon；
3) weigh the step 2) product of certain mass and pyrroles is mixed in the tetrahydrofuran solution of hydrochloric acid, add surface-active Agent polyvinylpyrrolidone and the 3h that stirs：Wherein：HCl mass fraction is 3.5% in hydrochloric acid；Hydrochloric acid and tetrahydrofuran Volume ratio is 0.6；
4) be slowly dropped into the hydrochloric acid solution of ammonium persulfate in the mixture of step 3), rate of addition control 0.5~ 4ml/min；0 DEG C of controlling reaction temperature, reaction time 8h；Agitation and filtration, drying etc., obtain polypyrrole/silicon composite；Over cure Sour ammonium is controlled 1: 1.3 with pyrroles's mass ratio；
5) product of the nickel acetate of weighing certain mass, stannous chloride and step 4) is mixed in hydrochloric acid；Add surface-active Agent polyvinylpyrrolidone stirs 5h：It is slowly dropped into sodium hydroxide solution, control solution pH value 5~9, reaction time 6h；Stirring Filtering, drying etc., obtain polypyrrole/silicon/nickel oxide/oxidation tin composite material；
6) step 5) product tabletting, inert atmosphere, 500 DEG C of heating 5h；Obtain nickel tin-carbon-silicon 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 nickel tin-carbon-silicon electrode material is：
Silica (nanosphere, specific surface area ＞ 700m2/ g), 0.05mol；Magnesium, 0.1mol；Thiophene, 0.1mol；Protochloride Nickel, 0.005mol；Tin acetate, 0.01mol；
Silica (nano powder, specific surface area ＞ 700m2/ g), 0.05mol；Magnesium, 0.2mol；Pyrroles, 0.25mol；Acetic acid Nickel, 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 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 (1)

  1. A kind of 1. preparation method of nickel tin-carbon-silicon electrode material, it is characterised in that：Using the silica of high-specific surface area as raw material, Mechanical mixture magnesium, high temperature thermal reduction, again acid treatment, coated with conductive polymer, deposited oxide nickel and tin oxide, tabletting, high warm Reduction, obtain nickel tin-carbon-silicon electrode material；The specific surface area of silica is more than 700m2/ g, for oxidation silicon nano power, silica Nanosphere, silica SBA-15, silica MCM-41, silica KIT-6 one kind；Conducting polymer be polyaniline, polypyrrole, One kind of polythiophene, polyacetylene；The mol ratio of silica and magnesium is 1: (2~4), silica rub with conducting polymer presoma You are than being 1: the mol ratio of (1~5), nickel oxide and conducting polymer presoma is 1: (1~20)；Nickel oxide and tin oxide rub You are than being 3: (1~8)；The preparation method of nickel tin-carbon-silicon electrode material comprises the following steps：
    1) silica and magnesium metal mechanical mixture of certain mass are weighed, then 600~800 DEG C of inert atmospheres thermal reduction 2~ 10h；
    2) step 1) product is immersed into excessive hydrochloric acid, reacts 2~40h, filtering, washing, drying, obtain porous silicon；
    3) step 2) product and polymer precursor are mixed in the organic solution of hydrochloric acid, surfactant is added and stirs 1~10h；
    Wherein：HCl mass fraction is 1~15% in hydrochloric acid；The volume ratio of hydrochloric acid and organic matter is 0.1~0.8；Organic matter For methanol, ethanol, ethylene glycol, glycerine, tetrahydrofuran one kind；
    4) hydrochloric acid solution of persulfuric acid thing is slowly dropped into the mixture of step 3), rate of addition is controlled in 0.5~4ml/ min；0~5 DEG C of controlling reaction temperature, 5~30h of reaction time；Agitation and filtration, drying, obtain polymer/silicon composite；
    Wherein, persulfuric acid thing is one kind of ammonium persulfate, sodium peroxydisulfate and potassium peroxydisulfate；Persulfuric acid thing and polybenzazole precursor constitution Amount is than control 1: (1~1.35)；
    5) soluble nickel salt, pink salt and the step 4) product for weighing certain mass are mixed in hydrochloric acid；Add surfactant stirring Uniform 1~10h：It is slowly dropped into sodium hydroxide solution, control solution pH value 5~9,1~10h of reaction time；Agitation and filtration, baking It is dry, obtain polymer/silicon/nickel oxide/oxidation tin composite material；
    Wherein, soluble nickel salt is nickel acetate, nickel nitrate, one kind of protochloride nickel；Soluble pink salt is nitric acid tin, protochloride One kind of tin, nitric acid tin；
    6) step 5) product tabletting, inert atmosphere, 400~900 DEG C of 1~5h of heating；Obtain nickel tin-carbon-silicon electrode material.
CN201510848744.3A 2015-11-21 2015-11-21 A kind of preparation method of nickel tin carbon-silicon electrodes material Expired - Fee Related CN105355888B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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