CN102339985A - Preparation method for anode material of lithium ion battery - Google Patents
Preparation method for anode material of lithium ion battery Download PDFInfo
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- CN102339985A CN102339985A CN2011102842068A CN201110284206A CN102339985A CN 102339985 A CN102339985 A CN 102339985A CN 2011102842068 A CN2011102842068 A CN 2011102842068A CN 201110284206 A CN201110284206 A CN 201110284206A CN 102339985 A CN102339985 A CN 102339985A
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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 for a tin-nickel-carbon anode material of a lithium ion battery. The method comprises the following steps of: 1, fully dissolving stannous chloride (SnCl2) into a cosolvent; 2, fully dissolving acetylacetone nickel into a cosolvent; 3, uniformly mixing the cosolvents obtained by the steps 1 and 2, and pouring the mixed solution into an ultrasonic vaporizer; and 4, causing vaporized aerial fog to enter a tube type heating furnace along with an inert gas, and instantly pyrolyzing the aerial fog and the inert gas to obtain the product. The tin-nickel-carbon composite nano material can remarkably ease serious bulk effects produced by the lithium intercalation and deintercalation of a tin-containing active substance, and has relatively higher reversible specific capacity and relatively longer cycle life.
Description
Technical field
The present invention relates to a kind of lithium ion battery negative material preparation method, be specifically related to the preparation method of tin nickel carbon negative pole material.
Technical background
In the high-end consumer electronic product, obtained using widely with the lithium ion battery of carbon (graphite) as negative material, aspect electric bicycle and electric automobile, using progressively increases.But the theoretical specific capacity of material with carbon element is merely 372 mAhg
-1, volume and capacity ratio also has only 800 mAhcm
-3About, with lithium metal 3860 mAhg
-1With 2060 mAhcm
-3Capacity differ greatly.In order to adapt to modern electronic equipment and the electric motor car growth requirement to the compact power supply of high power capacity, people have invested sight the research of new material.Some have the material of higher lithium storage content, and for example Sn, Si, Al, Sb and Ag etc. extensively and are in depth studied.
Most metals etc. all can form alloy with lithium, and these lists of elements reveal the reaction potential different with lithium, and theoretical specific capacity also has nothing in common with each other.Like Si is 4008mAh/g, and Sn is 994mAh/g, and Sb is 660mAh/g, and Al is 993 mAh/g.When but lithium and single metal form alloy, can be attended by very large volumetric expansion, huge volumetric expansion meeting causes electrode cycle performance variation, hinders its practical application in lithium ion battery.Carbon current clad nano metallic tin is a kind of desirable ion secondary battery cathode material lithium, but it seems with regard to present research situation, has many problems, faces a lot of difficulties.Wherein more topmostly be exactly; Tin is the very low metal of a kind of fusing point, and its fusing point has only 231.9 degree, if want a kind of metal is accomplished the process that carbon coats; Temperature at least will be more than 400 degree; But this higher relatively temperature can cause metallic tin to be difficult to be coated in the carbon shell, and the product that obtains will be the material that carbon tin separates, and can not reach desirable covered effect.In addition, present research is owing to receive preparation method's restriction, and this material can't synthesize on a large scale, causes application and development to relatively lag behind.
Summary of the invention
The objective of the invention is provides a kind of preparation method of lithium ion battery tin nickel carbon composite nano negative material to above weak point, and preparation technology is simple, cost is low, chemical property is good.
For this reason, the present invention adopts following technical scheme: it may further comprise the steps:
Take by weighing methyl alcohol or ethanol and nickel material in advance, the solubility pink salt mixes in beaker, obtains reactant liquor; The nickel in said methyl alcohol or ethanol and the nickel material and the mass ratio of the tin in the solubility pink salt are:
Methyl alcohol or ethanol: the nickel in the nickel material: the tin=1:0.01 in the solubility pink salt ~ 0.1:0.001 ~ 0.1;
Quartz ampoule is heated to uniform temperature, and feeds inert gas, keeping the interior temperature of pipe is 700 ~ 1500 degrees centigrade, the constant 0.1 ~ 0.5L/min of being of gas flow rate, and duration of ventilation is 0.5 ~ 1 hour;
The said reactant liquor for preparing is in advance put into ultrasonic atomizer, and gas flow rate is 0.5 ~ 1L/min in the increasing quartz ampoule, connects the ultrasonic atomizer power supply; React and stop heated quarty tube after 1 ~ 3 hour, keep the inert gas flow velocity constant till quartz ampoule is reduced to room temperature; Particle that obtains in the receiving flask or powder are cleaned, dry with methyl alcohol or ethanol.
Further, after getting nickel material, solubility pink salt and adding methyl alcohol or ethanol, ultrasonic atomizatio is nano particle or powder.
Said solubility pink salt is stannic chloride or stannous chloride.
Said nickeliferous material is nickel chloride or nickel acetylacetonate.
Prepared product filmed prepare half-cell behind the preparation work electrode.Being specially product, adhesive PVDF, conductive agent acetylene black are mixed by a certain percentage, is that solvent grinds evenly with the N-methyl pyrrolidone, is coated on the Copper Foil in vacuum drying oven with 80 ~ 120 degree drying 4 ~ 24 hours down.With this work electrode is positive pole, and the conduct of lithium sheet is to electrode, and electrolyte is EC/DMC (Vol 1:1) solution of the LiPF6 of 1M, and barrier film is polyethylene, polypropylene composite diaphragm.Test charging and discharging currents density is 0.2mA/cm2, is 0V-1.5V by charging/discharging voltage.
The present invention uses the vapour-phase pyrolysis legal system to be equipped with lithium ion battery tin nickel carbon compound cathode materials; The production process of this technology is continuous; Can be used for large-scale industrial production, and its restriction to raw material is less, can be used to prepare the molecule of various carbon-coated nano metallic particles and other types; In addition and since reactant in the high-temperature region time of staying short, avoided the product agglomeration, very suitablely be used for preparing this low melting point metal material of carbon-coated nano metallic tin.
It is carbon source that the present invention adopts industrial alcohol or methyl alcohol, is metallic tin nickel source with stannous chloride or stannic chloride, nickel acetylacetonate or nickel chloride, and the two copyrolysis is prepared carbon-coated nano metallic tin nickel material; Optimize synthetic technological condition, realize controlledization and designization product.
The present invention develops the production technology that a kind of electrochemistry capacitance height, good cycle, cost are low, be convenient to large-scale production; Firing rate is fast, the high temperature residence time is short; Can obtain that purity height, particle diameter are little, the nanometer tin nickel carbon particle of good surface activity, have great importance for the development of lithium ion battery.
Description of drawings
Fig. 1 is a process chart of the present invention.
Embodiment
Be described in further detail for the present invention through concrete embodiment below.
Embodiment 1
Quartz ampoule is heated to uniform temperature, and temperature is 1000 degree, the constant 0.2L/min of being of gas flow rate in feeding high-purity argon gas or the nitrogen maintenance pipe, ventilates 0.5 hour.
Put into ultrasonic atomizer, the methyl alcohol of the composition 1L that said reactant liquor is, 10g nickel acetylacetonate, 80g stannous chloride after the reaction liquid for preparing in advance stirred.
Strengthening the inert gas flow velocity is 0.5 ~ 1L/min, connects the ultrasonic atomizer power supply.The particle that obtains in the gatherer with methyl alcohol or ethanol clean, oven dry obtains tin nickel carbon nano-composite material, is lithium ion battery negative material.
The composite Nano negative material that more than makes is for anodal, and the lithium sheet is to electrode, and electrolyte is EC/DMC (Vol 1:1) solution of the LiPF6 of 1M, and barrier film is polyethylene, polypropylene composite diaphragm.Test charging and discharging currents density is 0.2mA/cm2, is 0V-1.5V by charging/discharging voltage.The composite Nano negative material of preparation capacitance first is 800mAh/g, and gram volume is basicly stable at 480mAh/g after 30 weeks.
Embodiment 2
Quartz ampoule is heated to uniform temperature, and temperature is 1200 degree, the constant 0.2L/min of being of gas flow rate in feeding high-purity argon gas or the nitrogen maintenance pipe, ventilates 0.5 hour.
Put into ultrasonic atomizer after the reaction liquid for preparing in advance stirred, said reactant liquor is methyl alcohol, 20g nickel acetylacetonate, the 100g stannic chloride of 1L.
Strengthening the inert gas flow velocity is 0.5 ~ 1L/min, connects the ultrasonic atomizer power supply.The particle that obtains in the gatherer with methyl alcohol or ethanol clean, oven dry obtains tin nickel carbon nano-composite material, is lithium ion battery negative material.
The composite Nano negative material that more than makes is for anodal, and the lithium sheet is to electrode, and electrolyte is EC/DMC (Vol 1:1) solution of the LiPF6 of 1M, and barrier film is polyethylene, polypropylene composite diaphragm.Test charging and discharging currents density is 0.2mA/cm2, is 0V-1.5V by charging/discharging voltage.The lithium ion battery negative material that present embodiment makes, capacitance is 750mAh/g first, gram volume is 398mAh/g after 50 weeks.
Claims (4)
1. the preparation method of a lithium ion battery tin nickel carbon compound cathode materials is characterized in that it may further comprise the steps:
Take by weighing methyl alcohol or ethanol and nickel material in advance, the solubility pink salt mixes in beaker, obtains reactant liquor; The nickel in said methyl alcohol or ethanol and the nickel material and the mass ratio of the tin in the solubility pink salt are:
Methyl alcohol or ethanol: the nickel in the nickel material: the tin=1:0.01 in the solubility pink salt ~ 0.1:0.001 ~ 0.1;
Quartz ampoule is heated to uniform temperature, and feeds inert gas, keeping the interior temperature of pipe is 700 ~ 1500 degrees centigrade, the constant 0.1 ~ 0.5L/min of being of gas flow rate, and duration of ventilation is 0.5 ~ 1 hour;
The said reactant liquor for preparing is in advance put into ultrasonic atomizer, and gas flow rate is 0.5 ~ 1L/min in the increasing quartz ampoule, connects the ultrasonic atomizer power supply; React and stop heated quarty tube after 1 ~ 3 hour, keep the inert gas flow velocity constant till quartz ampoule is reduced to room temperature; Particle that obtains in the gatherer or powder are cleaned, dry with methyl alcohol or ethanol.
2. the preparation method of used as negative electrode of Li-ion battery tin nickel carbon nano-composite material according to claim 1 is characterized in that: after getting nickel material, solubility pink salt adding methyl alcohol or ethanol, ultrasonic atomizatio is nano particle or powder.
3. according to the preparation method of any one described used as negative electrode of Li-ion battery tin nickel carbon nano-composite material in claim 1 or 2, it is characterized in that: said solubility pink salt is stannic chloride or stannous chloride.
4. according to the preparation method of any one described used as negative electrode of Li-ion battery tin nickel carbon nano-composite material in claim 1 or 2, it is characterized in that: said nickeliferous material is nickel chloride or nickel acetylacetonate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102945954A (en) * | 2012-12-12 | 2013-02-27 | 南京大学 | Preparation method of similarly-spherical Li(Ni1/3Co1/3Mn1/3)O2 precursor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101265571A (en) * | 2008-04-23 | 2008-09-17 | 华东理工大学 | Lithium ionic cell cathode silicon based compound material preparation method |
| CN101436657A (en) * | 2007-11-13 | 2009-05-20 | 比亚迪股份有限公司 | Composite material for lithium ion battery cathode and preparation method thereof, cathode and battery |
| CN101494284A (en) * | 2009-03-03 | 2009-07-29 | 清华大学 | Method for preparing nucleocapsid structure lithium ion battery alloy composite cathode material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101436657A (en) * | 2007-11-13 | 2009-05-20 | 比亚迪股份有限公司 | Composite material for lithium ion battery cathode and preparation method thereof, cathode and battery |
| CN101265571A (en) * | 2008-04-23 | 2008-09-17 | 华东理工大学 | Lithium ionic cell cathode silicon based compound material preparation method |
| CN101494284A (en) * | 2009-03-03 | 2009-07-29 | 清华大学 | Method for preparing nucleocapsid structure lithium ion battery alloy composite cathode material |
Non-Patent Citations (1)
| Title |
|---|
| ROCKSTRAW DAVID A.等: "Synthesis of Nanowires by Spray Pyrolysis", 《JOURNAL OF SENSORS》, vol. 2009, 31 December 2009 (2009-12-31), pages 1 - 3 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102945954A (en) * | 2012-12-12 | 2013-02-27 | 南京大学 | Preparation method of similarly-spherical Li(Ni1/3Co1/3Mn1/3)O2 precursor |
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