CN103219494A - Preparation method of graphite-ferroferric oxide composite cathode material - Google Patents
Preparation method of graphite-ferroferric oxide composite cathode material Download PDFInfo
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- CN103219494A CN103219494A CN2013101079815A CN201310107981A CN103219494A CN 103219494 A CN103219494 A CN 103219494A CN 2013101079815 A CN2013101079815 A CN 2013101079815A CN 201310107981 A CN201310107981 A CN 201310107981A CN 103219494 A CN103219494 A CN 103219494A
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Abstract
The invention relates to a preparation method of graphite-ferroferric oxide composite cathode material, and the method comprises the following steps of: (1) preparing an active substance Fe3O4; (2) uniformly coating a carbon layer on the surface of nano-silicon particle powder via the chemical vapor deposition method, then ball-milling and mixing the nano-silicon particle powder coated with the carbon layer, and graphite to obtain a high-reversible-capacity graphite mixture; and (3) weighing a specified amount of the active substance Fe3O4; adding dysprosium oxide, the high reversible capacity graphite mixture and PVA (polyvinyl alcohol) binder; and mixing substances uniformly to obtain the graphite-ferroferric oxide composite cathode material. The graphite-ferroferric oxide composite cathode material prepared according to the preparation method disclosed in the invention has the characteristics of integration of high capacity, high charge and discharge rate and high cycling stability due to combination of the ferroferric oxide composite cathode material with high specific capacity and the high reversible capacity graphite material.
Description
Affiliated technical field
The present invention relates to the preparation method of a kind of graphite-tri-iron tetroxide composite negative pole material.
Background technology
The energy is the important substance basis of human social development, but fossil energy storages such as coal, oil and natural gas fall sharply and make the mankind face the pressure of resource exhaustion, and problem of environmental pollution also is on the rise simultaneously.Therefore, the energy and environmental problem have become the focus that countries in the world are paid close attention to.Improve energy use efficiency, development and use regenerative resource, preserve the ecological environment, realize that sustainable development has become national governments and scientific research personnel's common objective and problem.Say that strategically the exploitation regenerative resource is solve energy problem basic, so the research work of this respect has been subjected to extensive concern, lithium ion battery is an important branch in the regenerative resource.The commercialization lithium ion battery generally adopts graphite material as negative pole, and its theoretical specific capacity only has 372mAh/g, and has the graphite linings peeling phenomenon in the fast charging and discharging process, causes tangible capacity attenuation; In addition, the embedding lithium current potential and the lithium deposition potential of graphite cathode material are approaching, be assembled into battery pack after, some monocell easily produces the Li dendrite phenomenon in the fast charging and discharging process, these factors all seriously restrict its application in power lithium-ion battery.Therefore, adopt other material to replace graphite cathode to become the emphasis of Study on Li-ion batteries using.
In recent years, it is found that some ferriferous oxide also can be used for lithium ion battery negative material, mainly comprises FeO, Fe3O4 and α-Fe2O3.This class material has specific capacity height, aboundresources, environmental friendliness and advantage such as cheap, and in addition, FeO and Fe3O4 also have electric conductivity preferably, are expected to be applied aspect high power lithium ion cell.The embedding lithium process of ferriferous oxide and other transition metal oxide negative material are similar.In three kinds of iron oxide materials, the theoretical specific capacity of α-Fe2O3 is the highest, is about 1005mAh/g, but the electric conductivity extreme difference, even when preparation is used for electrode slice that low-power discharges and recharges, also often need add the conductive agent about 40%, is difficult to realize commercial applications.Though the theoretical specific capacity of Fe3O4 is lower, be 745mAh/g only, electric conductivity is better, can be used for the high capacity type lithium ion battery negative material.Also need be more abundant but Fe3O4 takes off lithium, first charge-discharge efficiency has much room for improvement.
Summary of the invention
For overcoming above-mentioned deficiency, the invention provides the preparation method of a kind of graphite-tri-iron tetroxide composite negative pole material, use the negative material of this method preparation, have higher capacity, higher first charge-discharge efficiency and good cyclical stability.
To achieve these goals, the preparation method of a kind of graphite provided by the invention-tri-iron tetroxide composite negative pole material comprises the steps:
(1) preparation active material Fe
3O
4
With deionized water and frerrous chloride compound concentration is the solution of ferrous chloride of 1.5-2mol/L, with deionized water and potassium hydroxide compound concentration is the potassium hydroxide solution of 2-3mol/L, solution of ferrous chloride is heated to 95-99 ℃, the mode of potassium hydroxide solution with spray joined in the solution of ferrous chloride, in solution, blast simultaneously oxygen, by the time when new sediment occurring, do not stop to spray sodium hydroxide solution, the carbon black that adds frerrous chloride content 2-3% then, blast oxygen 20-40min again, filtration obtains sediment, and with deionized water washing sediment to saliferous acid group particle not, after the sediment oven dry, be put under 800-850 ℃ the condition and reduce, the material after the reduction was crushed to 30 mesh sieves, obtain active material Fe
3O
4
(2) preparation high reversible capacity graphite mixture
At first, method by chemical vapour deposition (CVD) is at nano silicon spheres powder coated with uniform charcoal layer, charcoal layer weight wherein accounts for 15-20%, concrete steps are: the nano silicon spheres powder is placed in the chemical gaseous phase stove, with nitrogen is carrier gas, flow rate of carrier gas is 200-300ml/ minute, under nitrogen protection, temperature in the chemical gaseous phase stove is risen to 750-850 ℃ with 5-10 ℃/minute heating rate, feed methane again, the volumetric concentration of methane is the 10-15% of carrier gas, carries out chemical vapour deposition (CVD), the chemical vapour deposition (CVD) time is 1-2h, and pressure is normal pressure;
The nano silicon spheres powder that will be coated with the charcoal layer again carries out ball milling mixing 3-6h with graphite, and ball milling speed is 300-400r/min, and nano silicon spheres grain weight amount wherein accounts for the 15-25% of mixture total weight, obtains the high reversible capacity graphite mixture;
(3) synthetic graphite-tri-iron tetroxide composite negative pole material
Take by weighing a certain amount of above-mentioned active material Fe
3O
4, press Fe
3O
4Amount place the dysprosia of 1-2wt%, the above-mentioned high reversible capacity graphite mixture of 10-15wt% adds and accounts for Fe
3O
4The concentration of 20-30wt% of amount be the 15-20wt%PVA binding agent, after stirring, obtain graphite-tri-iron tetroxide composite negative pole material.
Lithium ion battery graphite-tri-iron tetroxide the composite negative pole material of the present invention's preparation, with specific capacity higher-graphite material of tri-iron tetroxide composite negative pole material and high reversible capacity combines, and makes it have the characteristics of high power capacity, high charge-discharge speed and high cyclical stability concurrently.Therefore this composite material has higher capacity, discharges and recharges speed and long useful life fast when being used for lithium ion battery.
Embodiment
Embodiment one
With deionized water and frerrous chloride compound concentration is the solution of ferrous chloride of 1.5mol/L, with deionized water and potassium hydroxide compound concentration is the potassium hydroxide solution of 2mol/L, solution of ferrous chloride is heated to 95 ℃, the mode of potassium hydroxide solution with spray joined in the solution of ferrous chloride, in solution, blast simultaneously oxygen, by the time when new sediment occurring, do not stop to spray sodium hydroxide solution, the carbon black that adds frerrous chloride content 2% then, blast oxygen 20min again, filtration obtains sediment, and with deionized water washing sediment to saliferous acid group particle not, after the sediment oven dry, be put under 800 ℃ the condition and reduce, the material after the reduction was crushed to 30 mesh sieves, obtain active material Fe
3O
4
At first, method by chemical vapour deposition (CVD) is at nano silicon spheres powder coated with uniform charcoal layer, charcoal layer weight wherein accounts for 15%, concrete steps are: the nano silicon spheres powder is placed in the chemical gaseous phase stove, with nitrogen is carrier gas, flow rate of carrier gas is 200ml/ minute, under nitrogen protection, temperature in the chemical gaseous phase stove is risen to 750 ℃ with 5 ℃/minute heating rate, feed methane again, the volumetric concentration of methane is 10% of carrier gas, carries out chemical vapour deposition (CVD), the chemical vapour deposition (CVD) time is 2h, and pressure is normal pressure; The nano silicon spheres powder that will be coated with the charcoal layer again carries out ball milling mixing 6h with graphite, and ball milling speed is 300r/min, and nano silicon spheres grain weight amount wherein accounts for 15% of mixture total weight, obtains the high reversible capacity graphite mixture.
Take by weighing the above-mentioned active material Fe of 10g
3O
4, press Fe
3O
4Amount place the dysprosia of 1wt%, the above-mentioned high reversible capacity graphite mixture of 10wt% adds and accounts for Fe
3O
4The concentration of 20wt% of amount be the 15wt%PVA binding agent, after stirring, obtain graphite-tri-iron tetroxide composite negative pole material.
Embodiment two
With deionized water and frerrous chloride compound concentration is the solution of ferrous chloride of 2mol/L, with deionized water and potassium hydroxide compound concentration is the potassium hydroxide solution of 3mol/L, solution of ferrous chloride is heated to 99 ℃, the mode of potassium hydroxide solution with spray joined in the solution of ferrous chloride, in solution, blast simultaneously oxygen, by the time when new sediment occurring, do not stop to spray sodium hydroxide solution, the carbon black that adds frerrous chloride content 3% then, blast oxygen 40min again, filtration obtains sediment, and with deionized water washing sediment to saliferous acid group particle not, after the sediment oven dry, be put under 850 ℃ the condition and reduce, the material after the reduction was crushed to 30 mesh sieves, obtain active material Fe
3O
4
At first, method by chemical vapour deposition (CVD) is at nano silicon spheres powder coated with uniform charcoal layer, charcoal layer weight wherein accounts for 20%, concrete steps are: the nano silicon spheres powder is placed in the chemical gaseous phase stove, with nitrogen is carrier gas, flow rate of carrier gas is 300ml/ minute, under nitrogen protection, temperature in the chemical gaseous phase stove is risen to 850 ℃ with 10 ℃/minute heating rate, feed methane again, the volumetric concentration of methane is 15% of carrier gas, carries out chemical vapour deposition (CVD), the chemical vapour deposition (CVD) time is 1h, and pressure is normal pressure; The nano silicon spheres powder that will be coated with the charcoal layer again carries out ball milling mixing 3h with graphite, and ball milling speed is 400r/min, and nano silicon spheres grain weight amount wherein accounts for 25% of mixture total weight, obtains the high reversible capacity graphite mixture.
Take by weighing the above-mentioned active material Fe of 10g
3O
4, press Fe
3O
4Amount place the dysprosia of 2wt%, the above-mentioned high reversible capacity graphite mixture of 15wt% adds and accounts for Fe
3O
4The concentration of 30wt% of amount be the 20wt%PVA binding agent, after stirring, obtain graphite-tri-iron tetroxide composite negative pole material.
Comparative example
At first, adopt planetary ball mill and agate jar, it is 250rpm that rotating speed is set, and commercially available ironic citrate particle ball milling 3h is made the ironic citrate powder.Take by weighing the 1g commercial phenolic resin, join in the 5ml absolute ethyl alcohol, stirring a period of time forms flowability homogeneous phase solution preferably.Take by weighing 10g ironic citrate powder and under agitation adding in the above-mentioned solution, continue to stir a period of time until mixing, then 40 ℃ down heating be stirred to ethanol and volatilize fully.Change over to the gained brown powder in the beaker and be put in and be warming up to 120 ℃ in the drying box and solidify 4h, cooled cured granulate is pulverized, in 850 ℃ of heat treatment 4h, programming rate is 2 ℃/min in inert atmosphere.Taking-up is ground to sieve and is made the Fe/FeO composite negative pole material behind the natural cooling, crosses 400 mesh standard sieves.
Product in the foregoing description one, two and the comparative example is assembled into the CR2016 button cell respectively, with lithium sheet (Φ=16 purity〉99.9%) is to electrode, with polypropylene porous film (Φ=18) is barrier film, as electrolyte, the CR2016 battery is to finish in being full of the glove box of argon gas with the ethylene carbonate (EC) of LiPF6 and dimethyl carbonate (DMC) mixed solution (VEC:VDMC=1:1).Negative pole is to form with the The tape casting membrane, used slurry is that the embodiment one, two of 80% (mass percent) or the product in the comparative example, 10% PVDF solution, 10% conductive black, 1-Methyl-2-Pyrrolidone (NMP) mix, and the substrate of electrode film is a metal copper foil.At probe temperature is to carry out electric performance test under 25 ℃, and this embodiment one compares with the product of comparative example with two material after tested, and first charge-discharge speed improves 30-40%, improves useful life more than 2 times.
Claims (1)
1. the preparation method of graphite-tri-iron tetroxide composite negative pole material comprises the steps:
(1) preparation active material Fe
3O
4
With deionized water and frerrous chloride compound concentration is the solution of ferrous chloride of 1.5-2mol/L, with deionized water and potassium hydroxide compound concentration is the potassium hydroxide solution of 2-3mol/L, solution of ferrous chloride is heated to 95-99 ℃, the mode of potassium hydroxide solution with spray joined in the solution of ferrous chloride, in solution, blast simultaneously oxygen, by the time when new sediment occurring, do not stop to spray sodium hydroxide solution, the carbon black that adds frerrous chloride content 2-3% then, blast oxygen 20-40min again, filtration obtains sediment, and with deionized water washing sediment to saliferous acid group particle not, after the sediment oven dry, be put under 800-850 ℃ the condition and reduce, the material after the reduction was crushed to 30 mesh sieves, obtain active material Fe
3O
4
(2) preparation high reversible capacity graphite mixture
At first, method by chemical vapour deposition (CVD) is at nano silicon spheres powder coated with uniform charcoal layer, charcoal layer weight wherein accounts for 15-20%, concrete steps are: the nano silicon spheres powder is placed in the chemical gaseous phase stove, with nitrogen is carrier gas, flow rate of carrier gas is 200-300ml/ minute, under nitrogen protection, temperature in the chemical gaseous phase stove is risen to 750-850 ℃ with 5-10 ℃/minute heating rate, feed methane again, the volumetric concentration of methane is the 10-15% of carrier gas, carries out chemical vapour deposition (CVD), the chemical vapour deposition (CVD) time is 1-2h, and pressure is normal pressure;
The nano silicon spheres powder that will be coated with the charcoal layer again carries out ball milling mixing 3-6h with graphite, and ball milling speed is 300-400r/min, and nano silicon spheres grain weight amount wherein accounts for the 15-25% of mixture total weight, obtains the high reversible capacity graphite mixture;
(3) synthetic graphite-tri-iron tetroxide composite negative pole material
Take by weighing a certain amount of above-mentioned active material Fe
3O
4, press Fe
3O
4Amount place the dysprosia of 1-2wt%, the above-mentioned high reversible capacity graphite mixture of 10-15wt% adds and accounts for Fe
3O
4The concentration of 20-30wt% of amount be the 15-20wt%PVA binding agent, after stirring, obtain graphite-tri-iron tetroxide composite negative pole material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702938A (en) * | 2016-04-15 | 2016-06-22 | 华南师范大学 | Iron-based oxide lithium ion battery negative electrode material and preparation method and application thereof |
| CN113793924A (en) * | 2021-08-25 | 2021-12-14 | 浙江工业大学 | By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material |
| CN114141993A (en) * | 2021-11-25 | 2022-03-04 | 广东凯金新能源科技股份有限公司 | Processing technology of composite modified graphite negative electrode with good cycling stability |
| CN114141993B (en) * | 2021-11-25 | 2024-05-03 | 广东凯金新能源科技股份有限公司 | Processing technology of composite modified graphite negative electrode with good cycle stability |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645505A (en) * | 2008-11-03 | 2010-02-10 | 成都和能科技有限公司 | High-capacity iron electrode material |
| CN101924196A (en) * | 2009-06-17 | 2010-12-22 | 中国科学院金属研究所 | Method for greatly improving reversible capacity of graphite |
| CN102427129A (en) * | 2011-12-12 | 2012-04-25 | 浙江大学 | Lithium ion battery composite negative electrode material, its preparation method, negative electrode with application of material thereof and lithium ion battery |
| US20120231340A1 (en) * | 2009-11-20 | 2012-09-13 | Sumitomo Chemical Company, Limited | Transition-metal-containing hydroxide and lithium-containing metal oxide |
-
2013
- 2013-03-31 CN CN2013101079815A patent/CN103219494A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101645505A (en) * | 2008-11-03 | 2010-02-10 | 成都和能科技有限公司 | High-capacity iron electrode material |
| CN101924196A (en) * | 2009-06-17 | 2010-12-22 | 中国科学院金属研究所 | Method for greatly improving reversible capacity of graphite |
| US20120231340A1 (en) * | 2009-11-20 | 2012-09-13 | Sumitomo Chemical Company, Limited | Transition-metal-containing hydroxide and lithium-containing metal oxide |
| CN102427129A (en) * | 2011-12-12 | 2012-04-25 | 浙江大学 | Lithium ion battery composite negative electrode material, its preparation method, negative electrode with application of material thereof and lithium ion battery |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702938A (en) * | 2016-04-15 | 2016-06-22 | 华南师范大学 | Iron-based oxide lithium ion battery negative electrode material and preparation method and application thereof |
| CN113793924A (en) * | 2021-08-25 | 2021-12-14 | 浙江工业大学 | By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material |
| CN113793924B (en) * | 2021-08-25 | 2023-03-14 | 浙江工业大学 | By using supercritical CO 2 Preparation of Si/Fe by fluid medium 3 O 4 Method for preparing/C composite material |
| CN114141993A (en) * | 2021-11-25 | 2022-03-04 | 广东凯金新能源科技股份有限公司 | Processing technology of composite modified graphite negative electrode with good cycling stability |
| CN114141993B (en) * | 2021-11-25 | 2024-05-03 | 广东凯金新能源科技股份有限公司 | Processing technology of composite modified graphite negative electrode with good cycle stability |
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Application publication date: 20130724 |